Alain received Charizard when it was still a Charmander from Professor Sycamore when Alain was still working with him. It was shown in a flashback that it battled against Lysandre's Pyroar when it was a Charmeleon, 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 Chariazrd used Steel Wing, but was countered by Mega Absol's Megahorn. Mega Charizard repeated the attack, hitting Mega Absol. Mega Chariazrd 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 back 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 megalith. 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 megalith. Mega Charizard targeted Primal Groudon for attacks, leaving Steven's Mega Metagross to handle Primal Kyogre. Primal Groudon used Solarbeam, 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 megalith, 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 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.
When the heroes tried to discover more about Ash's Greninja's power, they encountered Alain. To find out more about the power, Ash challenged Alain to a battle once more, using his Greninja against Alain's Mega Charizard X. However, up to the point where Greninja pushed too hard on using its unique form, Ash collapsed to the ground and the battle was called off immediately.
|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)