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Electivire debuted in The Eighth Wonder of the Sinnoh World! where it was the first Pokémon which Volkner used during his rematch against Ash. Ash first used Torterra, but it was easily defeated thanks to Electivire's Ice Punch. Next Ash chose to use Pikachu. With his Thunderbolt, Pikachu triggered Electivire's Motor DriveAbility, making it an even harder target to hit. However, when one of Electivire's punches connected with Pikachu, the Thunderbolt Pokémon was paralyzed by Pikachu's Static. After this, Pikachu was able to finish Electivire with a well-aimed Iron Tail.
Electivire reappeared in Ultra Exciting from the Shocking Start!, when it was the third Pokémon in his World Coronation Series match against Ash. It was used to negate Pikachu's Thunderbolt with its Motor Drive Ability. After Pikachu, it briefly battled Ash's Lucario before being recalled. Electivire later battled Ash's Pikachu again, but it was eventually defeated by Pikachu's 10,000,000 Volt Thunderbolt, which proved to be too much for Motor Drive to absorb.
Electivire is one of Volkner's toughest Pokémon who has been specifically trained to combat Pokémon who have the advantage against Electric-types by using moves such as Ice Punch to counter Ground-types. Besides Volkner's Raichu, it seems to be one of his most trusted Pokémon and used for many important battles and often spends time off-battling with its Trainer, seen in The Fiery Road to Mastership! where it watched Cynthia's battle at the Masters Eight Tournament.
Electivire debuted in Shorting Out Electivire and he was described as being Volkner's most powerful Pokémon, being called out to face off against Platinum's Rapidash to not only to test Platinum's strength following her run-in with Team Galactic's Jupiter, but also for the Beacon Badge. He used Thunder Punch on Rapidash, which shattered the ground, but it has little effect on Rapidash, prompting Platinum to call out the weak attack and Electivire is subsequently defeated by Platinum and thus she earns the Beacon Badge.
In The Final Dimensional Duel VI, Electivire and Flint's Magmortar battled together against the Legendary PokémonGiratina, attacking with Discharge and Lava Plume respectively, but Giratina shrugged off the attacks with ease and sweeped Electivire and Magmortar off their feet with a Dragon Breath, knocking them out. Electivire and Magmortar later managed to get their revenge on Giratina in The Final Dimensional Duel XI when they landed a sneak attack on it as Giratina was attempting to ambush Platinum, Diamond, and Pearl from behind.
