Yes, of course!
First off, it is important to understand the concept that there are two sides to administering any WordPress site; that the management of the framework and/or the content require two separate approaches and tool sets. Once this concept is understood, things get much clearer when you work with WordPress.
WordPress uses themes to set the design or layout of a web site. You can choose from, literally, hundreds of different styles and layouts for your site. Once you have chosen a theme, that theme can be further modified to better suit your needs, if desired.
To modify the layout or appearance (formatting) of a site, you would use Dreamweaver (or any capable web page editor) to modify your chosen theme’s php files and css file(s). Normally, once a site’s framework and/or appearance is set up, there are few requirements to make further changes. It is important to note that any mistake in changes to the php/css coding could have disastrous consequences.
WordPress does have the ability to work on these files directly, BUT, the file’s permissions have to be changed to allow this AND, Dreamweaver is a much better tool to do this with, so why would one do this through WordPress (unless you were away from your Dreamweaver enabled desktop)
To create, modify, update or delete the site CONTENT (pages, posts, categories, links, etc. and/or text/images within those pages/posts), you would do this through the WordPress administration panel. WordPress writes the new or updated content into the database on the fly. The FRAMEWORK created above provides structure and formatting for the CONTENT that you create for display to your web visitors.