If the word "OR" appears between the names, it's clear that the check can be negotiated by either payee. Whether your bank will allow Smith to cash it may be affected by policy, but he should be able to deposit it to his personal account or the account of the business. I don't imagine, though, that you'll see that sort of check very often.
If the names are stacked and there's no conjunction between them, the intent of the check's issuer is ambiguous. The UCC directs in such cases that you can treat it as if "OR" appears.
Take care, though. Sometimes the second name is preceded by "c/o." That stands for "care of," and is a signal that everything that follows is part of the address instruction on the check, and the name after "c/o" is not a payee.
I should add here that many banks have policies that require all named payees to endorse a check when it's ambiguous whether the payees are named alternatively or not. That's the bank's right, since it's not required to accept the check for deposit or cashing other than on its own terms.
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John S. Burnett
BankersOnline.com
Fighting for Compliance since 1976
Bankers' Threads User #8