An LLC can be sole proprietor (single member), partnership, or corporation so the LLC designation alone is not indicative- it is always best to ask if not 100% sure. You can get a copy of a W9 from the IRS website and give it to them- if they do not normally get 1099-MISCs because they are a corporation, they will let you know.
The number one reason you must be diligent and at least ask (and not assume) is that if you should have issued the 1099-MISC and did not, you can be fined and it is possible (but not likely) that the IRS can deny the deduction so you would have to pay the taxes on the entire deposit.
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