When I started all I used was the browser and a text editor like Notepad++. I actually just finished a web design program where they went through all the Adobe tools including Dreamweaver and I wouldn't recommend that for learning. It's too easy to fall prey to letting it do the work for you which isn't great for learning.
Now I use Sublime Text 2 and Chrome browser/DevTools. Simple, effective, cheap. I do use Photoshop for complex designs but if I'm just messing around or trying things out, nothing beats the speed of just typing up a .html file and a .css file and refreshing the browser to see the changes.
Also, I used to run into problems with things not always looking the same in Dreamweaver as they did in an actual browser.