Vista Keyboard Shortcuts
Killer list of Vista keyboard shortcuts here.
My favorite - launch any application by hitting the WinKey and then start typing the name (e.g. Word) hit enter and it launches. This is absolutely awesome.
I can't stand trying to find an application by navigating through the Start Programs menu. Now I never have to do it again!
I used to use a tool called Launchy to do this in Windows XP. If you're still on XP I highly recommend checking it out!
