Froakie first appeared when he observed Pikachu shocking Bonnie, Clemont and Ash outside the Lumiose Gym. It followed the group to a nearby park, where it watched the trio talking from a tree. When the group were attacked by Team Rocket, Froakie protected Pikachu from its own Electro Ball, which had been rebounded by Wobbuffet's Mirror Coat. He then used the sticky bubbles on his back, called Frubbles, to hit Wobbufet, and helped Ash defeat Team Rocket. After Team Rocket were sent blasting off, Froakie fainted and Ash took him to Professor Sycamore's lab.
Eventually, Froakie was healed at Sycamore's lab. Froakie was present when Team Rocket tried to take control of Professor Sycamore's Garchomp and assisted Ash in his attempt to help. When Garchomp was about to fall off the Prism Tower, Froakie used his Frubbles to stick Garchomp's feet to the floor and prevent it from falling. This then allowed Pikachu to destroy the machine controlling Garchomp with Iron Tail. At the end of the episode, Froakie appeared in front of Sycamore's lab with a Poké Ball and asked Ash to catch it, which Ash did so gladly.
In A Battle of Aerial Mobility!, Froakie quickly attacks a Fletchling that made Bonnie cry and a Dedenn leave, despite Ash telling him to stand down and let Pikachu attack. Fletchling easily evades every attack and almost knocks Froakie out with a devastating Razor Wind, but Ash pushes him away to save him. Although the group is intially mad, they learn of Froakie's motives, and make a plan for him to take down Fletchling.
They lure Fletchling to an area with many rocks at many levels, which allows to use Froakie to move freely and be on even grounds with the flying type. However, Fletchling's aeiral speed allows him to evade all of Froakie's attacks, although Froakie evades his just as well. Fletchling then gets a solid hit on a hidden Froakie, that was actually a fake made of frubbles. Froakie then finally lands a hit with his newly learned Bubble, and Ash attempts to capture it, but fails. Froakie then evades the powerful Razor Wind and finishes Fletchling off with Water Pulse, allowing Ash to capture it.
Froakie is used again in Battling on Thin Ice!, using his frubbles for Pikachu and Froakie to dodge, in preperation for Ash's rematch against Viola. In Clemont's Got a Secret!, Froakie is sent out to battle Clemont's Magnemite and Magneton, and despite the type disadvantage, Froakie single handedley incapacitates them with his Frubbles. In An Appetite for Battle!, Froakie is used to battle Clemont's Chespin for practice since Chespin was getting lazy and obese, but Froakie overcame another type disadvantage and easily beat it with his new Pound attack.
Later, Froakie was used to battle Sanpei and his Frogadier. But because of Frogadier's intense speed and power, it lost. Froakie then tried to become super fast and strong by trying to learn Quick Attack. However, when Team Rocket attacked, it instead learned Double Team.
Froakie was then used to battle Grant's Onix in Ash's second Kalos gym battle, which Froakie successfully did when a newly formed strategy called the Rock Tomb Climb. Froakie then battled Grant's Tyrunt but was easily defeat with a powerful Draco Meteor.
Froakie was later used to battle a Hawlucha Ash made friends with after settling a rivalry with a Machamp. However, the battle ended when Hawlucha's Flying Press collided with Froakie's Pound attack, knocking both Pokémon out in a draw.
Sometime later, Froakie was doing some training sessions with Ash and his Pikachu. But when a log came hurdling down from a waterfall, Froakie defended Pikachu's life and learned Cut to stop the log from falling on Pikachu. Froakie later got into a squabble with Hawlucha and began to fight each other. Their fighting didn't last long until a Trevenant kidnapped Ash and dragged him into the forest. When Froakie and Hawlucha attempted to save their trainer, they learned that the reason why Trevenant kidnapped Ash is because it needed his help in saving its companions, a Bonsly and a Sudowoodo, who were caught in an electric net set up by Team Rocket. Hawlucha and Froakie both worked together to save the two Pokémon, send Team Rocket flying, and settle their differences, becoming best friends in the process.
Froakie seems to be a tough Pokémon in reference to his personality. He left many of his previous trainers as his natures didn't meet with them. He finally chose Ash after seeing his bravery. Froakie even has the tendency to blush when it is thanked and praised by other Pokémon and people. For example, when it used its frubbles to tidy up Fennekin's tail, it thanked Froakie for its thoughtfulness.
|Water Pulse||Kalos, Where Dreams and Adventures Begin!|
|Bubble||A Battle of Aerial Mobility!|
|Pound||An Appetite for Battle!|
|Double Team (move)||A Rush of Ninja Wisdom!|
|Cut||Forging Forest Friendships!|
|+ indicates this Pokémon used this move recently.*|
- indicates this Pokémon normally can't use this move.
- Froakie's capture marks the first time since catching Heracross that Ash's first capture in a region has not been of the Flying-type.
- However, Heracross does have the ability to fly.
- Kalos is the second region where Ash catches one starter Pokémon, Froakie. The first is Hoenn where Ash catches Treecko.
- Froakie is the first of Ash's Pokémon to be owned by more than one trainer before its capture by Ash.
- Froakie is Ash's eighth Pokémon to battle its evolved form. The other eight were Pikachu, Sceptile as a Treecko, Corphish, Buizel, Gliscor as a Gligar, and Snivy, Piginte as Tepig before it, and Fletchinder as Flecthling after it.