PokéBase - Pokémon Q&A
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I'm Horde EV Training my Riolu and so it started to evolve while I was training. So I'm wondering if evolving him during training will mess stats or something up?

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No.

Pokémon stats are calculated with a formula that takes into account several factors - base stats, IVs, EVs, level, and natures. Of these, only the base stats are modified by evolution (though likely the Pokémon also leveled up before it evolved); its effort values will remain unchanged and you can raise them in exactly the same way as before. It will have precisely the same stats at level 50 whether it evolved at level 50 or 10, so long as it gained the same effort points.

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Ok, thank you.
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No
It will not
Source : experience

edit : unless there was a move you wanted it to learn that is unable to be learned by it's evolutions

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