Froakie first saw Ash when he fell down the Prism Tower and continued to observe the gang until Team Rocket intervened in Ash and Clemont's friendly Pokémon battle. It volunteered to help out by successfully using the white bubbles from its cape to counter Jessie's Wobbuffet but ended up receiving quite a bit of damage during the encounter. Ash then decided to take it to Professor Sycamore's lab, where it was treated and restored to full health.
Later on, when Team Rocket attempted to use a ring-type device against it but a Garchomp got caught in the middle, while rescuing Froakie, and went berserk as a result of the device malfunctioning. Ash, along with his Pikachu and newly befriended Froakie, heads out to rescue Garchomp. In order to prevent Garchomp from falling down the Prism Town, it uses the white bubbles from its cape on Garchomp's feet and Pikachu breaks the device using Iron Tail.
While leaving Professor Sycamore's laboratory, Froakie throws a chunk of white bubbles in Ash's face in order to get his attention. It was standing alongside a Poké Ball on the floor in front of it, expressing its desire to join his party. Froakie then happily presses the Poké Ball's button and gets captured.