PokéBase - Pokémon Q&A
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I have a level 100 Gardevoir and I wish to reset its EVs with a reset bag. But I don't wanna do the boring and long Super Training, instead I wanna do EV training from Wild Pokemon. So I was wondering if a level 100 Pokemon can still gain EVs through battling wild Pokemon.

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Short answer:

Yes.

>Pokémon can now gain effort values from battling even at Level 100

More on EVs

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THANKS!