PokéBase - Pokémon Q&A
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The other day i was looking for a shiny pichu in the trophy garden, i used the poke'radar and battled 22 pichu's (before the chain was broke) with my scyther (adamant nature and proud of it's power behavior) and he was holding the power belt to ev train for defence, but when scyther leveled up he gained 13 Sp.Def.

Does chain battling (or what ever it's called when you fight the same pokemon over and over again) increase the amount of ev's you gain when leveling up?

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does your scyther have pokerus and are you sure it wasn't speed that got the +13?  i honestly can't answer the question but if you were tired or not paying much attention when you leveled maybe you miss-read the slot that it was in because pokerus + 22 pichu's would give 11 speed and the level could give two by itself maybe.
did you battle/chain anything else before this?

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Chaining doesn't give you anything extra special, except for the fact you're battling the same Pokemon over and over so you get the same EVs. However, Pichu gives off Speed EVs and the Power Belt add 4 Defense EVs each battle.

So either you battled several Pokemon with Sp.Def EVs while your Scyther was the same level, or you were actually holding the Power Band.

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