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Empoleon debuted in the same episode as his trainer, where he battled Ash's Pikachu. Although it proved to be a powerful opponent, Pikachu managed to defeat Empoleon. Empoleon would later battle Pikachu again in order for a chance for Barry to battle Palmer, but Pikachu won a second time.
While Barry trained on Iron Island, Empoleon, like all other Steel type Pokémon on Iron Island (except Riley's Lucario), went crazy due to the activities of Team Galactic. When the villains left the island, Empoleon returned to his normal self.
On another occasion, Barry used Empoleon to battle a wild Gible though Barry ended up commanding it to blast Gible away before he could catch it. After Ash caught Gible, Barry decides to battle it with Empoleon. Drill Pecks and Steel Wings hit Gible in a fashion it utilizes simultaneously. When Gible dodged Empoleon's Hydro Cannon with Dig, Empoleon used Hydro Cannon again in the hole, creating an eruption of light. Empoleon sends an unmastered Draco Meteor with Steel Wing at Piplup. Empoleon used Hyper Beam against Dragon Pulse. When Gible is tired, Empoleon wins the battle with Hyper Beam.
In Fighting Ire with Fire, Empoleon battles Ash's Monferno. Empoleon starts with Drill Peck, but is hit by back-to-back Mach Punchs and Digs. Empoleon finishes Monferno off with Hydro Cannon. Before, it was seen knocking out a Mothim with its newly learned Metal Claw.
Empoleon was used during Barry's battle against Paul, where Empoleon blasted his Magmortar with Hydro Cannon so Paul recalled Magmortar. Empoleon was recalled when Paul sent out Ursaring. After Barry's Hitmonlee was defeated, Empoleon briefly fought Ursaring, who was then replaced by Electivire. Empoleon fought bravely, activating Torrent during the battle in a final desperate attempt to defeat Electivire, but Electivire blocked its Hydro Cannon with Protect and knocked out Empoleon with a powerful Thunder.
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|Hydro Cannon +||Barry's Busting Out All Over!|
|Hyper Beam +||Barry's Busting Out All Over!|
|Steel Wing +||Barry's Busting Out All Over!|
|Hydro Pump||Jumping Rocket Ship!|
|Drill Peck +||Gotta Get a Gible!|
|Metal Claw||Fighting Ire With Fire!|
|+ indicates this Pokémon used this move recently.*|
- indicates this Pokémon normally can't use this move.