Dreamweaver is great. However Dreamweaver also costs a lot of money. In search for a free solution you might end up in several places, but two of the well-known options are Nvu or Kompozer, a web-authoring and editing software that is certainly not unfamiliar to those that went to college or attended University courses related to IT, especially web-design. Is it (Kompozer is actually a newer release of Nvu) as good as Dreamweaver? Yeah, well, that depends mostly on what you’re looking for. Admittedly the new CS 5.5 Dreamweaver is quite amazing, so it’s sort of hard to compete with, but I’d say Kompozer is the next best solution (if you do find something better, let me know, please) to amateur and junior web-design. Why amateur? Well, I don’t know how to put this, but an experienced designer will only use even DW more as a tool than a complete suite and workflow basis. Once you get the hang of web-coding and design, you do tend to downgrade to hand-written code, so these programs are more of a first step into the fabulous World of web-design.
LE: Due to the high number of new web technologies, the introduction of HTML5, CSS3, responsive design and their adoption at a never seen before rate, Kompozer and many of the other free alternatives tend to be at best a worst case scenario alternative, thus producing safe to publish code only in very simple scenarios. Make sure you understand the risks and their limitations.