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Example: Shuckle 252def with Power trick. Should I put that EVs in attack or will Power trick also take EVs?

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Since, EVs affect the stats, and Power Trick switches the Pokemon's stats, technically yes.

If you put 252 EVs in Defense, that would increase your Defense stat by 63 points, raising it to a hypothetical 614 from a stat of 551 with no EVs. Power Trick takes the value of 614 and switches it with its Attack value of, say, 22.

So now the Shuckle's attack would be 614, and the Shuckle's defense would be 22.

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Your forgetting about natures Shuckle can't have an maximum Attack Stat of 130 and a maximum Defense Stat of 614 :P
Derp... lemme fix that
Thank you very much!