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Vee first appeared in Blame it on Eevee. When Red tried to challenge Erika, she stated that she wouldn't battle him unless he was able to capture a Pokémon of her choice, an Eevee. Red, with the help of Bill, tried to battle Vee, but for every Pokémon that was sent out Vee would turn into the Eeveelution that had a type advantage over it. This ability confused both of them at first, but Bill eventually figured out the ability, and Red managed to discover a way to keep Vee from sensing the type of Pokémon sent out. Red was thus able to capture the Eevee. Realizing that his body had been experimented on to allow such an ability, Red took the Eevee to the Celadon Gym and connected it to a healing machine to allow him to recover. Just then, Erika appeared once again, and feigned being a member of Team Rocket to force Red to fight for him. Despite Saur, Poli, and Pika's best efforts, Erika was able to counter their abilities one by one with her variety of movesets, and then approached Vee, saying that if she disconnects him now, he would surely take his last breath. Red, evoking his deepest desire to defend the poor Pokémon, had Pika use a Substitute clone to distract Erika while having him guard the healing machine. Erika, impressed with their valiance, revealed herself to be an ally of the "good" Gym Leaders he had met before, and not only awarded Red the Rainbow Badge but also allowed him to keep Vee.
Vee was later used alongside Red's other Pokémon to battle Team Rocket members who were pursuing Articuno in the Seafoam Islands, which they ultimately failed to defend. Soon afterwards, Red sent Vee into storage after restoring Aero in Cinnabar Island. It was later discovered that when Red had sent him to Professor Oak, Vee had been captured by Team Rocket again. Later on, Red rescued Vee in The Winged Legends, after the evil Sabrina had no use for him, as she had now obtained the merged legendary birds. Two years later, Red also used Vee to battle Bruno on Cerise Island, taking advantage of his ability to change into his evolutions, which was enhanced through the three Vermilion Harbor evolutionary stones he obtained from Giovanni. A combination of its powers as Vaporeon and Jolteon allowed Red to take the win.
Vee was used on Red's test to become Viridian City's Gym Leader, defeating the last of the Association's Pokémon, Porygon2. It was his first appearance as an Espeon, and although he was not identified as Vee, Red expressed that he clearly had much trust in the Pokémon. Red later explained to Sabrina that the Pokémon was in fact Vee but that he had lost his ability to change into his Fire, Water, and Electric-type evolutions upon evolving into Espeon. Though it had now become a normal Espeon, Red still preferred it this way that it isn't burdened by the sufferings of his past any longer.
A † shows that the move was used recently, unless all moves fit this case or there are fewer than five known moves.
In the anime
Red's Jolteon in Pokémon Origins
In Pokémon Origins
Red uses a Jolteon in the Pokémon Origins mini-series. It is one of his most used Pokémon in the mini-series, being one of the few Pokémon besides his Charizard that he is seen using in more than one episode.
Red was seen using Jolteon again in File 3 - Giovanni, where he sent it out against Giovanni's Rhyhorn during his Gym battle against the Rocket Boss. However, like Red's Victreebel, Kabutops, and Snorlax before it, Jolteon was defeated before could land a single hit on the Spikes Pokémon.
Red also used Jolteon at the Indigo Plateau in File 4 - Charizard. It first appeared during Red's battle against Lorelei and her Dewgong, presumably defeating its opponent off-screen. Later, during Red's final battle against the Champion, Blue, the Lightning Pokémon was seen facing Blue's Pidgeot before eventually falling to Blastoise's Skull Bash.