yes. google "remap mydocuments folder" and it'll show you examples. you can remap mydocs, mypics, myvids, mydownloads, etc onto another hard drive, and it's a "permanent" remapping. quite handy. part of the remapping process is that windows will automatically move any existing content, so you don't need to do any work ahead of time. just make a new folder, remap, wait, and see it complete.
or click here: http://support.microsoft.com/kb/310147