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I second the php.net manual (I added it as a search engine in firefox). I also found "PHP and MySQL Web Development (Welling/Thomson)" useful; However, I find the best learning method (for me) is the head-against-wall-repeat technique, coupled with a whole lot of googling, and a sprinkling of online tutorials.
I would also recommend a firm grasp of HTML/CSS before venturing forth, as it seems a lot of folks skip this step and end up paying the piper later.
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