I've gone through the preferences but can't see anything obvious, searched the web, tried disabling the anitvirus/firewall stuff (AVG/Sygate Personal) but it hasn't helped. Anyone know how to fix it?
EDIT: Solved it. Just in case anyone comes across this message and has the same problem, here're the details...
I happened to try it later on the same computer but while logged in as a different user. That username wasn't used much since the XP install really - plain ol' desktop etc. Dreamweaver worked fine there!
While logged in as that user I looked at the startup details in msconfig to compare them to those used while logged in as my own username. But even making sure mine matched as much as possible didn't help. Yet still DW wouldn't work under my username but would under that. It became clear...
I save documents of various types or download programs (or even install if it's just a peice of shareware I might remove later) a LOT to the desktop/My documents folder. My desktop was a repository for many folders.
Windows loading my 650MB+ profile with my username versus loading the username with its <70 meg one caused DW to choke. So (logged in as administrator on the PC obviously) I created a new user via the control panel. I could then use that instead and DW is now a-ok. The old user files (my saved docs etc) are still safe on the machine - I can delete them later if I like. It solved the issue immediately.
I also pledged to make sure in future to save stuff NOT to the desktop or my documents (and thus make the Windows profile huge) but to c:\anyfolders only!