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Empoleon first appeared along with Barry in Barry's Busting Out All Over! where it was revealed to be a strong Pokémon in a battle against Ash's Pikachu. However, after a hard-fought battle, it lost the match. It was revealed in the same episode that Barry had Empoleon by the time he challenged the Eterna City Gym, where it fought a very hard battle against Gardenia's Cacnea and won.
It fought Ash's newly obtained Gible in Gotta Get a Gible!, where it won, giving Barry his first victory over Ash. It appeared again in Fighting Ire with Fire!, where it started a battle with Ash's Monferno, due to the activating of Blaze, the battle had no conclusion.
Empoleon's next appearance came in League Unleashed!, where it got Barry through the preliminaries of the Lily of the Valley Conference after defeating another Trainer's Nosepass. In Casting a Paul on Barry!, it was used in Barry's battle against Paul. It battled against Paul's Magmortar briefly before Paul recalled his Pokémon, then Barry recalled Empoleon. It was used again to fight against Paul's Ursaring, where it was able hit a Focus Blast back to Ursaring before Paul recalled Ursaring for his newly evolved Electivire. Empoleon eventually activated Torrent after a long battle and then used Hydro Cannon. However, Electivire used Protect and was soon defeated by a powerful Thunder, making Barry lose the battle. It fainted standing up.