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I'm trying to get a black sludge on ultra sun but whenever I use thief on the Pokemon that can have it, they mainly faint so I am worried that this is preventing me from getting the item.

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No, it should work after your enemy faints because there will be some dialog saying that your Pokémon stole an item.

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Yes it will still work.

I know this from experience, as I used this method to get Heart Scales from Luvdisc in ORAS, and I doubt the mechanics have changed since then. I suggest leading with a Pokemon with the ability Frisk, though, as it will mean you are not wasting your time attacking Pokemon that aren't holding an item.

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Even though you're probably just getting unlucky, I would recommend you check to make sure your Pokémon isn't holding anything, since that will prevent Thief's secondary effect.