Dreamweaver Site Definition for Drupal Theme Development
You should have at least one sites defined in your Dreamweaver installation for testing your themes. To define sites click site, new site. An ideal site definition for Drupal theme is like this. Note:- I assume that you have installed Drupal locally. Else refer these articles 'How to Install Drupal on an XAMPP installation' and 'Installing a Local Web Server'
Local info

Remote info

Testing Server

If you have more than one site defined select the one under which you want the theme files to be placed.