PokéBase - Pokémon Q&A
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I know vitamins have a base value of 10 EVs and you can have a total of 252 in one stat. I tried to give 26 proteins to my Pokémon that is right out of the daycare, but it will only let me give it 10 proteins and after that it says it has no effect. Am I missing something here? I’ve been EV training in the newest gen, but I’m not sure if Gen 4 is different in that aspect. If anyone can help out it would be a great help.

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A Pokémon cannot use a vitamin if they have 100+ EVs in that stat.

Between Generations III and VII, vitamins will also have no effect on an individual stat that already has 100 or more EVs.

Hope I helped!

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What I don’t understand is that this Pokémon is fresh from an egg. Does it already have 100 EV values in Gen 4? I have not leveled it up or anything. I even tried giving it a different vitamin but it also had no effect after I gave it 10 vitamins.
Once you give it 10 Proteins, it increases the Pokémon’s Attack EVs to 100, if it’s fresh from an Egg. From then on, you can’t give it any more Proteins. Pokémon from an Egg do not hatch with EVs. However, you could give it 10 Carbos for example, since Carbos give 10 Speed EVs each.
Ohh so you can only give them 10 vitamins in one stat and rest will have to be EV trained from wild Pokémon?
That’s correct.
Okay thank you a bunch. Sorry for any confusion.
If you had 99 EVs and used a vitamin would you get to 109 or 100
https://m.bulbapedia.bulbagarden.net/wiki/Effort_values

“Vitamins add 10 effort points. Prior to Generation VIII, they could not raise a stat above 100 EVs.”