It depends on what you want to do and how involved you want to get. The "[Progam] For Dummies" books are popular and I like the "Teach Yourself [Program] In 24 Hours" and "[Program] Weekend Crash Course" books. (Various publishers and authors.) Once you learn some stuff, the "Visual Quickstart" series of stuff is a good reference to flip to a specific thing.
For beginners, FrontPage holds your hand fairly well. Dreamweaver MX is very powerful, but is overwhelming for beginners. What are you planning on doing?
Webmonkey is a good resource and I'm sure others will suggest other places.
While it's also important to learn some basic HTML, DO NOT get beating by the old-school macho web coders who prowl around here and thump their chests and grunt, "Ungawa!!! Use Notepad! Real man use Notepad!" Yeah, right, why the heck spend the time hacking out:
<table border="0" cellspacing="0" cellpadding="0">
<tr align="left" valign="top"> <td><img src="/support/dreamweaver/images/icon_dw_oneline.gif" width="55" height="45" alt="Dreamweaver Icon"></td>
<td><img src="/support/dreamweaver/images/h1_using_css.gif" width="350" height="58" alt="Macromedia Dreamweaver Support Center - Using Cascading Style Sheets"></td>
</tr>
</table>
...when you can use a layout app to do the grunt work?!? It's not a replacement for knowing some coding, but sheesh, life's too short!