How to teach XHTML, CSS, and PHP?

My little brother asked me to teach him XHTML, CSS, and PHP.

I’m not really a teaching type person, meaning I have a hard time figuring out the best way to teach someone how to do something.

I really want to help him out and am wondering what is the best way to go about teaching him the basics?

The way I learned was by tearing apart others code and making it my own, slowly (sometimes quickly) learning what each function was and what it did. A lot of reading on PHP.net’s awesome documentation.

The upside to that was I learned at my own pace and I feel I have a good idea what I’m doing.
The downside is that sometimes it took me a while to figure out what was going on, also I learned bad programming habits from looking at others bad programming.

I feel that this wouldn’t be a good way to send him since looking back it was hard for me at some points, and I want him to utilize what I’ve learned through the years.

Any ideas?