Dreamweaver CS5: The Missing Manual, is a very comprehensive guide to building a website using Dreamweaver CS5.
It is written in a style that makes it easy for relatively basic computer users, to go through step by step. However it is also written in enough depth to satisfy those with a need to go beyond to basic.
Once thing that would be great to have added into the book would be a guide on how to easily setup for instance a blog, or incorporate some other website features. Whilst this wouldn't necessarily fall under the heading of learning Dreamweaver's functionality, combined with the rest of the book it would prove an invaluable guide for anyone wishing to set up a website.
A good book, that can be skim read and can be read out of order (IE. the most relevant chapter to ones needs can be read first.)