Leon Kilat at The Cybercafe Experiments has instructions on how to edit a WordPress theme using Dreamweaver.
WordPress, like most PHP-MySQL CMS, use template files to control the appearance of websites. The webpage is assembled from several PHP files controlling specific aspects of the site like the header, sidebar, main content and footer.
To use Dreamweaver to edit or customize WordPress themes, you need to combine these different PHP files into one page so that you can immediately view, while editing the codes, how the page would appear.
I think it is an overly complex way of editing WordPress themes, but for those that love Dreamweaver and don’t feel comfortable in anything else, have a look at this little tutorial.