PokéBase - Pokémon Q&A
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So if I accidentally go into battle with a random pokémon and send out one that I'm ev training, will it get evs when it goes into battle or after I win.

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I think it's after the enemy pokemon dies
You have to defeat the Pokémon to receive the EVs.

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[EVs] are primarily obtained by defeating Pokémon in battle, based on the Pokémon that was defeated.

However, in battles that do not give any experience (such as in the Battle Tower or if the Pokémon is level 100), Pokémon will not gain any effort points.

Effort Values (Bulbapedia)

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