I'd probably break it down into two segments, a basic Q&A session about the job, with some PHP, SQL and basic (but always standards-compliant) HTML and CSS questions. Shamittomar has provided a link to a good set of PHP questions and I would highly recommend using them.
Once this part is done and their brains feel thoroughly warmed-up I would give them two tasks to do.
- Write a basic script of your choosing, something that the business already uses that should only take a small amount of time to complete. You're hiring someone to write code, so they should be able to write basic PHP code fairly easily. Give them a blank computer with a clear history and tell them you'll be watching them, and after the test you'll be viewing what resources they use to get the problem sorted. Obviously, someone who can work his way around PHP.net to find whatever documentation he/she needs isn't entirely stupid.
- Fix a fairly complex script that you have written, provided only with a basic specification, descriptions from you of what the script is to do and a broken script you have pre-prepared. My last boss used to do this by writing a script himself, taking a note of every mistake he made and adding them back in at the end; at least that way the code itself wasn't broken beyond repair.
I find this to be the best compromise between simply looking at examples of code they're written and giving a full Joel Spolsky style interrogation. Give an applicant this test and you'll more than likely find someone with the level of competence you require, or someone who really isn't far from what you need.