As high performance languages and frameworks like Node.js and Scala become more popular, is it even worth learning a seemingly old school language like PHP? Considering the persistent demand for PHP developers, and the fact that the language is in use as sites like Facebook and Wikipedia, I'd say so. ChartBoost recently posted an article called "Running a Modern Startup on PHP" on its blog.
Furthermore, popular platforms like WordPress, Drupal and Joomla are all based on PHP. If you want to want to customize these applications, or build plugins, you'll need to know PHP. And though you don't have to build Facebook applications with PHP, it's helpful know it when developing on that platform anyway.
Here are some resources to help get you started.
Build Your Own Database Driven Web Site Using PHP & MySQL
Sitepoint's Build Your Own Database Driven Web Site Using PHP & MySQL by Kevin Yank is a lucid introduction to both PHP and MySQL for the non-programmer. The full book costs money, but Sitepoint offers the first 168. You'll have to fork over your e-mail address to get it, though.
However, you can much of the material on the Web in this series of tutorials by Yank.