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A Buneary used switcheroo and gave my trevenant assault vest. How is that possible?


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Quite simple really. It lies in the ability
One of Buneary's abilities is Klutz. What does this do?
>Klutz prevents use of held items on the Pokémon with the Ability. It disables the battle effect of the held item, rather than preventing an item from being held.

So this negates Assault Vest's effect of not allowing you to use non-offensive moves, so it can destroy your life with Switcheroo now.

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Before you get all excited about this amazing new strategy, note that this is essentially taunt, except it takes up your item slot and boosts the opponent's special defense. The only advantage is removing their item and being able to use this on an aroma veiled pokemon.