Dreamweaver have this bad habit of freezing itself once in a while, specially at the start up like a stubborn old horse. I tried all sort of remedies adobe suggested in here, even the most common one, uninstall and reinstall everything, which normally took hour or two of my time every Monday morning.
Finally I found this remedy which so far working pretty well for me. All you have to do is, go to the windows registry HKEY_CURRENT_USER/Software/Adobe/Dreamweave CS4/Temp File List/ and delete all the entries there, like they are your sworn enemies. And Dreamweaver will be ready for another day of fine coding.