From my experience learning PHP isn't hard. I've learned it in a week. But I had a strong C programming base.
If you need to learn it from the beginning, well, it might be harder. You need to know at least a base of HTML (or XHTML) and of basic, not the language, Programming (An, eventually, a basic knowledge of SQL). Obviously every good modern website will also need CSS for page formatting and some AJAX (by using a framework such as jQuery) to do some neat "Web 2.0" stuff.
I know this is a collection of C tutorials to start, but I think it would give you an idea on how to program: Basic C Programming Tutorials. I'd also buy a book like Learn to Program by Pragmatic Bookshelf. Or, if you like to try something different to learn programming itself and a "peculiar" programming language, I'd go for why's (poignant) guide to ruby. It's great and it starts from the beginning. I would also take a look at this reply on StackOverflow: it contains lots of free eBook and guides to a lot of programming languages (There are also two for PHP) and to programming itself. A great resource, IMHO.
However you might find useful the Official PHP Manual. I've used this to start working on PHP and I think it's the best if you use it. It has every update to the language and lots of example for each functionality of the language.
I don't know if learning by yourself would be effective as learning from taking instructions. In my experience learning by your own takes you as high as write simple programs. But then, when you want to do more difficult stuff, you have to try to write your application (Or web site, all right) and then go around the web and ask for help (Here might be a good place).
All right, now get yourself a copy of XAMPP and get to work!