We need clarification on the difference between a form 8233 and a W-8BEN. When should we use which form?

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8233 is used when a non-resident alien (i.e., individual) is making a treaty claim on U.S. source services income.  If the payee is not an individual, or the payment is not for services, or there is no treaty claim, then the 8233 would not be the correct form.  (It can also be used to claim a personal exemption on non-employee compensation if no treaty is available, but this does not occur much outside of the colleges and universities setting.)

The Form W-8BEN is used by individuals to document their non-U.S. status, and to make treaty claims on U.S. source income that is not services (e.g., royalties, interest, etc.)

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