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I am trying to learn about the EVs used in Pokemon to boost stats.

If a pokemon is just caught, does it have no EVs at all? Does this also hold true for pokemon obtained in different ways such as breeding? Do special pokemon [like Mewtwo or Shaymin] and Shiny pokemon start with zero EVs?

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Yes, Pokemon's EVs start at 0 when caught and they have since gen 1:

The Pokémon data structure contains two EV bytes for each the five stats (HP, Attack, Defense, Speed and Special), starting at zero when caught

Shinnies are just palette-swapped and don't get an EV boost, bred pokemon inherit IVs from their parents, as noted here but not EVs.

EVs are always manually obtained by a trainer; they're Effort Values so there's no way to gain them other than grinding or Vitamins . In Gen V you can also raise effort values using the Wing items.

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    Vitamins and wings can increase EVs, but you could argue that that's just grinding of another sort.
    – Shinrai
    Apr 12, 2012 at 19:54
  • Vitamins are limited to 10 per use. You can boost an attribute to a maximum of 255 EV pts, but is only worth 252 because they give bonus at 4 only. so you can have two attributes in 252 and one with 6. With wings you can boost without limit, but they are not in the shop you need to "farm" them on the bridge.
    – Michel
    Apr 13, 2012 at 14:11
  • @MichelAyres true, I was just trying to drive home that only player actions on a captured pokemon increase EV, they always start at 0
    – Ben Brocka
    Apr 13, 2012 at 14:38

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