In this thread you can see some of the issues getting Dreamweaver to connect to Magento with live data. I am not even sure that dhbyrne ever got it to work.
Mostly I work with the .phtml template files with my favorite editors and generally test and work things out on a test server install. I do use dreamweaver, but it’s a little bit of a run around, and I prefer never to let dreamweaver produce code for me. What I do to use dreamweaver during the design phase is get the html output from magento and create a static version of the pages that I can then link to the CSS, JS, and Images that are going to be used. After making the design changes to the static pages I have a model to work from, then I take the altered html and place it back into the template files that magento uses, however - this can be tricky because there are a many layers to the template files and there are a lot of things like this: <?php getChildHtml('content') ?> that turn into something like this in html:
<p>Here is content written in the admin panel</p>
It seemed to me that that trying to get dreamweaver to link into the php files, database, and all the other bits that make magento was a lot harder than diving into the files with WordPad or a similar text editor and getting an understanding about how it all works together. Dreamweaver can’t make heads or tails out of the XML layout files for one example, nor will it write any of them for you without some serious customization to dreamweaver itself - if that’s even possible. That’s not to say that you can’t use dreamweaver to design some wonderful pages, but it won’t produce anything magento can use on it’s own and without you doing some hands-on coding to get the output from dreamweaver into a form that magento can use.
On the other hand, after a few weeks of playing around with the template system in magento I have found that the process is fairly easy to understand and doesn’t require any advanced skills - use the many available free templates on Magento Connect as a library of samples, and put your thinking cap on and you will find that the process is not as difficult as you might initially view it.