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I just ev trained my froslass, ingame Platinum, for SpA and Speed evs after breeding so it had zero evs after hatching. I battled few random battles to balance out a bit but after that I specifically only battled specific Pokemons purely for SpA and Speed ev training. After about 100 encounters with wild mons, I checked to see if I can feed it calcium and it said it wont have any effect which means it should have maxed 252 evs for SpA and so did for carbos which means I have 6 evs left to use up. I used kelpsey berry to remove attack evs to ensure I have full 6 to contribute to my HP but I was able to feed HP up more than 5 times and even several irons and zincs. How is this even possible?

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More then Likely, your stats weren't maxed like you thought. From Gen 3 to Gen 7, vitamins did not affect any stat that was already above 100evs. Depending on the Pokémon you battled it's likely you were just over the ev threshold thus making them unaffected by your vitamins. In your scenario, it would be better to give your vitamins before battling Pokemon for max effect.

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Hope I Helped.

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