I've used both...
I find myself using GoLive all the time. I tried to switch, because I heard the DreamWeaver had more functionality to it's code, but after much testing, I found Dreamweaver just has a different set of problems. I ended up switching back becuase I like Adobe's interface. Seems kind of a lame excuse to cause a switch, but it didn't take much for me to switch in the first place, so I guess it shouldn't have to take much to switch back.
If you know HTML, you can always de-bug from either programs "source" window. I've stuck with GoLive since they made the revision to not rewrite the source code. That was really messing up my CDML tags at the time.