The code Word produces is horrid. If you just want to make a quick and dirty web page with it, there's no reason why you can't, but you'll more than likely will have to rebuild your page from scratch, rather than just opening and editing in Golive Dreamweaver (although Dreamweaver does have a handy "Clean Up Word HTML" command). There may also be an issue with Word-generated pages not displaying properly in every browser... but I don't use Word for html so I wouldn't know for sure.
If you have Fireworks or ImageReady (comes w/ Photoshop), I would suggest building your page from there. You simply create the page layout in Fireworks or ImageReady, create "slices" around your graphics/buttons, and these apps will export your web pages for you.
But if Word is easier for you at the moment, you may as well go with that.