After Charmander evolved, it battled against Lysandre's Pyroar, but it lost. Lysandre told Alain he could achieve greatness if he became the strongest - hence why he offered a Charizardite for Charmeleon and a Key Stone for Alain.
Charizard was used in a battle against Astrid and her Absol. Absol used Psycho Cut to counter Flamethrower and used Megahorn, but Charizard blocked the attack. Both Pokémon Mega Evolved and started an intense battle. Mega Charizard used Steel Wing, but was countered by Mega Absol's Megahorn. Mega Charizard repeated the attack, hitting Mega Absol. Mega Charizard used Dragon Claw. Mega Absol used Dark Pulse to counter Mega Charizard's Flamethrower, but Mega Charizard used Blast Burn, defeating Mega Absol in an instant. Charizard later faced Remo and his Mega Garchomp. Remo believed Alain to be claiming lies, saying Charizard was a dragon-type Pokémon. Alain Mega Evolved Charizard, proving his fact. Garchoo used Dragon Rush, hitting Mega Charizard, who retaliated with Flamethrower. Mega Garchomp used Dual Chop and clashed with Mega Charizard's Dragon Claw, but Mega Garchomp got defeated. Alain used Charizard against yet another Mega Pokémon, this time Siebold and his Blastoise. Mega Charizard dodged Blastoise's Hydro Pump and tried to hit it with Dragon Claw, but missed. Blastoise used Skull Bash, but Mega Charizard used Dragon Claw to counter the move. Siebold Mega Evolved Blastoise, whose Dragon Pulse, that was powered by its ability Mega Launcher, dealt a lot of damage to Mega Charizard. Mega Blastoise used Hydro Pump, hitting Mega Charizard, who endured the attack, exchanging blows by using Flamethrower against Mega Blastoise's Power-Up Punch. Mega Charizard managed to hit Mega Blastoise with Dragon Claw, but was defeated by its Dragon Pulse.
Alain challenged Steven Stone for a battle after seeing his Mega Stickpin. Alain used his Mega Charizard while Steven used his Metagross. Mega Charizard started off with Flamethrower, though Metagross used Psychic to cancel the attack. Steven Mega Evolved his Metagross, who used Flash Cannon to hit Mega Charizard. Mega Charizard used Dragon Claw, hitting Mega Metagross, who retaliated with Meteor Mash, bashing Mega Charizard onto a rock. Mega Charizard used Blast Burn, but Mega Metagross was not affected, while Steven warned Alain not to underestimate Metagross. When the two Pokémon were about to clash with Dragon Claw and Meteor Mash, a Flamethrower interrupted the battle and both Pokémon stopped with battling and reverted to their normal forms. It was revealed that Lysandre was the one who interrupted the battle. When Mega Rayquaza appeared, Alain used his Mega Charizard to stop Mega Rayquaza from attacking the shrine that consisted of the Giant Rock. Mega Charizard used Flamethrower, but Mega Rayquaza dodged the attack and attacked Mega Charizard with Dragon Ascent. Mega Metagross managed to save Mega Charizard before Mega Rayquaza used Draco Meteor to destroy the ruins.
Alain used his Charizard again when Groudon and Kyogre were battling against each other for the Giant Rock. Mega Charizard targeted Primal Groudon for attacks, leaving Steven's Mega Metagross to handle Primal Kyogre. Primal Groudon used Solar Beam, but missed Mega Charizard, who used Flamethrower. Primal Groudon attacked with Precipice Blades, though Mega Charizard crashed through the rocks with Dragon Claw. Mega Charizard used Steel Wing, but was badly injured by Groudon's Precipice Blades and crashed into the iced land. Alain went to Charizard and saw that the flame on its tail became smaller and retrieved Charizard so it couldn't take more damage. After the battle around the Giant Rock, Alain asked Lysandre for more battles, wanting to get much stronger. Lysandre allowed him so and Alain sent Charizard to battle a trainer's Mega Tyranitar.
Both Alain and Charizard wanted to become stronger, so Lysandre thought of a challenge. The challenge consisted of ten Mega Evolution trainers; Alain accepted the challenge, but was warned if he was defeated even in a single challenge, he'd had to hand over his Key Stone and Charizardite to Lysandre. In the battle against Mega Venusaur, Mega Charizard used Flamethrower, but Mega Venusaur took less damage due to Thick Fat and poisoned Mega Charizard with Venoshock. Mega Venusaur used Vine Whip, binding Mega Charizard and slamming it to the ground. Mega Charizard managed to free itself and repel Mega Venusaur's Seed Bomb and defeat it with Dragon Claw. After the battle, Alain gave a Pecha Berry to Charizard, who ate it, curing its poison status. Before Mairin could speak to Alain, a new challenger came, who sent and Mega Evolved Alakazam. Mega Alakazam used Psycho Cut, hitting Mega Charizard, who retaliated with Dragon Claw. After defeating Mega Alakazam and Mega Aggron, Mairin approached Alain, who brushed her off. After Mairin ran away, Charizard wasn't very pleased of how Alain handled and Alain noticed it. After Mega Charizard defeated a Mega Pinsir with Dragon Claw, Alain faced his last challenger: the Elite Four, Malva and her Houndoom. Mega Charizard used Flamethrower, which Houndoom absorbed with Flash Fire before being Mega Evolved. Mega Houndoom used Flamethrower, hitting Mega Charizard and filling the area with Smog. Mega Charizard used Flamethrower to clear the smoke and proceeded to attack with Steel Wing, but was hit by Mega Houndoom's Crunch, knocking Mega Charizard on the floor. Mega Charizard freed itself with Flamethrower. Mega Houndoom used Dark Pulse, which Mega Charizard tried to counter with Dragon Claw, but got hit by Crunch. The Mega Pokémon used Flamethrower attacks, which collided. Mega Houndoom attempted to defeat Mega Charizard with Crunch, but Mega Charizard summoned a great load of power and defeated Mega Houndoom with Blast Burn. Both Charizard and Alain were happy when they succeeded in completing the challenge. After Alain took off on his mission to gather more energy to recover Chespie, Alain and his Charizard faced a trainer who had a Mega Banette.
Alain, who has been watching Ash, sent Charizard to battle Team Rocket, freeing Pikachu from their robotic arm by using Dragon Claw. Team Rocket was angry, but were blasted off by Pikachu's Thunderbolt. Later on, Alain sent Charizard to battle Ash's Greninja. Greninja started off with Water Shuriken, but Charizard negated the move by using Dragon Claw. Charizard dodged Greninja's Cut and burned him with Flamethrower. Wanting to get Greninja to show off its power, Alain had Mega Evolve Charizard. Greninja countered Mega Charizard's Dragon Claw attack by Cut, then used Double Team. Mega Charizard banished the illusions with Flamethrower. Greninja attempted to use Aerial Ace, but got hit by Thunder Punch. Greninja rose up and transformed itself, syncing its mind and feelings with Ash. Greninja used Aerial Ace, hitting Mega Charizard. Mega Charizard attempted to attack with Thunder Punch, but Greninja used Cut to counter the move. To finish the battle, Mega Charizard launched Blast Burn, defeating Greninja in an instant.
Per Lysandre's request, Alain sent Charizard to attack Z-2 (in its serpent form), to help Aliana and Mable capture it for Team Flare's purposes. After Charizard hurt Z-2 with Dragon Claw, Alain Mega Evolved it. Z-2 managed to use Extreme Speed and bash Mega Charizard into a wall, who retaliated with Dragon Claw. Z-2 retaliated with Land's Wrath, an attack Mega Charizard managed to endure. During this distraction, Aliana and Mable managed to drain Z-2's energy and capture it properly. Charizard, however, shifted into its original form, since Alain finished the task.
Once Greninja recovered from its battle against Clemont's Luxray, Ash sent him in a battle against Alain's Charizard. Charizard countered Greninja's Water Shuriken and banished illusions (created by Double Team) with Flamethrower. After Greninja managed to execute Cut on Charizard, Alain Mega Evolved it. Mega Charizard attempted to use Thunder Punch, but missed and got hit by Greninja's Aerial Ace. Greninja tried to use Cut, but was blocked by Flamethrower and blown away by Thunder Punch. Greninja stood up and transformed itself. While Mega Charizard managed to counter Cut with Flamethrower, it got hit by Greninja's Aerial Ace. Mega Charizard managed to push away Greninja with Dragon Claw, a pain Ash sensed. While Greninja managed to attack Mega Charizard, Ash felt strange and collapsed, thus ending the battle. Later on, Alain saw Charizard was looking forward to battle Ash and Greninja once more.
Alain challenged Korrina for a Gym Battle for his final badge with his Charizard against her Lucario. They Mega Evolved their Pokémon, to which Mega Lucario made the first attack with Aura Sphere, but Mega Charizard used Flamethrower, which clashed with it. Unfortunately, Mega Lucario was defeated and Korrina gave Alain the Rumble Badge, to which she wished him good luck for the League.
Alain used his Charizard in the first round of the Lumiose Conference against Trevor and his Charizard. Trevor's Charizard started the battle by using Fire Spin and Alain's Charizard was able to dodge the attack by flying up. Alain's Charizard then used Flamethrower but Trevor's Charizard blocked the attack by using Dragon Claw. After blocking the attack, Trevor Mega Evolved into his Mega Charizard into Mega Charizard Y and used Heat Wave. Alain's Charizard slammed its tail on the water, using the water to block Heat Wave, and Trevor's Mega Charizard used Dragon Tail. Alain's Charizard dodged the attack by flying up and Alain Mega Evolved his Charizard into Mega Charizard X. Alain's Mega Charizard used Flamethrower while Trevor's Mega Charizard used Fire Spin and the two attacks collided, creating some smoke. Trevor's Mega Charizard flew towards Alain's Mega Charizard but Alain saw what Trevor's Charizard was trying to do and ordered his Charizard to use Flamethrower towards Trevor's Mega Charizard, defeating the latter. After defeating Trevor's Mega Charizard, Alain's Mega Charizard easily defeated Trevor's other two Pokémon, Aerodactyl and Florges, with Flamethrower. A part of this battle was shown in a TV show, hosted by Malva.
Alain faced Remo and had Charizard defeat his fifth Pokémon, a Rhyperior, with Dragon Claw. Remo recalled his first encounter with Alain and sent Garchomp and Mega Evolved it. Garchoo fired Draco Meteor, which hit Charizard, whom Alain Mega Evolved. Mega Charizard used Dragon Claw, which clashed with Garchoo's Dragon Rush. Mega Charizard, however, tossed Garchoo away and burned it with Flamethrower. Garchoo tried to use Dragon Claw, but Mega Charizard used the same attack and defeated Garchoo. Alain's Mega Charizard shifted into its original form and was called back by Alain, who walked away victoriously from the battlefield. Alain continued training his Charizard for the Kalos League finals. During the night, Sycamore came to Alain and noted how powerful Charizard was.
To battle against Pikachu, Alain sent Charizard. However, Pikachu damaged Charizard immediately with Quick Attack and electrocuted it with a super-effective Thunderbolt. Pikachu used another Thunderbolt, which hit Charizard. Just as Pikachu was unable to use Quick Attack, Charizard fired Flamethrower, which burned the former. The latter repeated its attack, which Pikachu negated by slamming Iron Tail on the ground and raising the rubble to stop the attack. After his Bisharp was defeated, Alain sent Charizard back into the fight to face Ash's Greninja. Both Pokémon charged towards each other, though Greninja used Cut and hit Charizard. While Ash's Greninja, through Bond Phenomenon, transformed himself, Alain Mega Evolved his Charizard. Ash-Greninja used Double Team, though the illusions were banished by Mega Charizard's Flamethrower. Next, Ash-Greninja fired Water Shuriken, which was countered by Mega Charizard's Dragon Claw. Ash-Greninja came close to Mega Charizard and attacked with Aerial Ace, but got pushed away by its Dragon Claw. After negating Mega Charizard's Flamethrower with Cut, Ash-Greninja slammed its Water Shuriken into the ground to stop Mega Charizard's Blast Burn. This surprised Mega Charizard, who immediately got hit by Aerial Ace. Still, Mega Charizard counterattacked with Dragon Claw, inflicting some more damage on Ash-Greninja. Mega Charizard used another Dragon Claw, which was stopped by Ash-Greninja's Cut. Mega Charizard then used Thunder Punch, but failed to hit Ash-Greninja, who used Water Shuriken to negate the attack and wound Mega Charizard. Ash-Greninja conjured a golden Water Shuriken and threw it to Mega Charizard, who fired Blast Burn. After the collision, Ash-Greninja fell down in defeat, while Alain's Charizard, managing to stay standing, won the battle, earning Alain the victory of the Kalos League finals.
Ash and Alain were searching for Mairin, as the roots spouted out throughout Lumiose City. Alain sent out his Charizard, who used Flamethrower to burn away the roots, but failed. Even with Ash's Pikachu's power combined, Charizard was unable to destroy the roots, which only regrew back. After Ash and Greninja broke free from Lysandre's cuffs with Bond Phenomenon, Charizard freed the rest of Ash's Pokémon. Alain Mega Evolved his Charizard, as he and Ash faced Lysandre. Mega Charizard used Dragon Claw, but was hit by Lysandre's Mega Gyarados' super-effective Stone Edge. Mega Charizard used Dragon Claw on Mega Gyarados and wounded it, along with Ash's Hawlucha's High Jump Kick. Later, it used Thunder Punch and hurt Mega Gyarados. Just as Talonflame and Ash-Greninja launched their attacks, Mega Gyarados used Stone Edge and hit them both. Mega Charizard saved them from falling down, but they all got hit by Mega Gyarados' Dragon Tail.
After a hard battle, Mega Charizard used Dragon Claw, Ash-Greninja used Cut and Pikachu fired Thunderbolt, which managed to successfully defeat Mega Gyarados. Later, Mega Charizard was later sent out to help Serena's Braixen, who nearly fell down from Mega Metagross. It also used Flamethower on the plants to free Steven's Mega Metagross, to fight against the Giant Rock. In the process, Greninja managed to track Chespie's location within the artificial creature and used Water Shuriken to show everyone where it is. Mega Garchomp fired another Flamethrower, but was soon bound by the Giant Rock's plants. When it seemed that Greninja, Braixen, Charizard, Mega Garchomp, and Mega Metagross were about to face their doom, the Kalos Gym Leaders and Diantha showed up with their Pokémon.
After strategizing their plan of saving Chespie, everyone combined their powers to fight off the Giant Rock. As they were running towards the Giant Rock, Alain had Mega Charizard fire Flamethrower on the roots to bun them away. Ash and Alain reach into the core and rescue Chespie, thus bringing the Giant Rock to a halt. However, when everyone tried to destroy the Giant Rock, Lysandre showed up and resurrected the creature with his remote control. Ash-Greninja, Pikachu, and Mega Charizard managed to destroy Lysandre's remote, which allowed Squishy and Z-2 to destroy the Giant Rock and finish Lysandre off once and for all.
After Team Flare's evil ambitions were finally put to an end, while not wearing its Key Stone, Charizard assisted Greninja in rescuing Pikachu from Team Rocket by using Flamethrower. Charizard and its trainer received Honor of Kalos medals for their heroic efforts against Team Flare.
When Alain accepted the offer to become Professor Sycamore's assistant, his Charizard no longer Mega Evolved, due to Alain giving his Key Stone and its Charizardite to the authorities as evidence of Lysandre's crimes. Alain told Ash that he would start over again from the beginning and his effort to find a new Key Stone and a Charizardite for his Charizard.
|Flamethrower +||Mega Evolution Special I|
|Steel Wing||Mega Evolution Special I|
|Dragon Claw +||Mega Evolution Special I|
|Blast Burn +||Mega Evolution Special I|
|Thunder Punch +||A Meeting of Two Journeys!|
|+ indicates this Pokémon used this move recently.*|
- indicates this Pokémon normally can't use this move.
- Kiyotaka Furushima (Japanese as a Charmander and a Charmeleon)
- Kensuke Satō (Japanese and English as a Charizard)
- Tom Wayland (English as a Charmander and a Charmeleon)
- ^ a b Pokémon: Mega Evolution Special I
- ^ a b Pokémon: Mega Evolution Special II
- ^ Pokémon: Mega Evolution Special III
- ^ Pokémon: Mega Evolution Special IV
- ^ XY106: A Meeting of Two Journeys!
- ^ XY107: An Explosive Operation!
- ^ XY116: The Synchronicity Test!
- ^ XY118: Championing a Research Battle!
- ^ MS019: Pokémon The Movie - Volcanion and the Mechanical Marvel
- ^ XY123: A Diamond in the Rough!
- ^ XY125: A League of His Own!
- ^ XY126: Valuable Experience for All!
- ^ XY127: Analysis Versus Passion!
- ^ XY129: Kalos League Passion with a Certain Flare!
- ^ XY130: Finals Not for the Faint-Hearted!
- ^ XY131: Down to the Fiery Finish!
- ^ XY132: A Towering Takeover!
- ^ XY133: Coming Apart at the Dreams!
- ^ XY134: The Right Hero for the Right Job!
- ^ XY135: Rocking Kalos Defenses!
- ^ XY136: Forming a More Perfect Union!
- ^ XY137: Battling with a Clean Slate!
- ^ XY140: Till We Compete Again!