I should say though, I did this for a while under Windows 7 and it did screw up a few things. See how you go, but it would better to relocate your larger folders for each user, rather than relying on symlinks.
Once it's working you can right click on Documents, Downloads, Desktop, etc, and move them using the "Location" tab (use a Different folder on your E Drive... not your Sym linked folder). Windows will copy all the data for you and update all the appropriate pointers. Then you can move the Users folder (should be smaller) back to your system drive.