Where should one start on the path to freelance web design/development?

Here’s the situation: I’m a graphic designer by the fact that that’s what my degree is in, but I’m the photo editor of a retail website. It’s dead end and I’d like to combine my interest in web technologies and graphic design into something more meaningful.

I’d like to know where you would suggest I start? What tools do I need? I’ve done a fair amount of redesigning blog templates in CSS, but haven’t created anything from scratch. My knowledge of HTML is serviceable. PHP? Ajax? Something I’ve never heard of?

Thanks!