Should work, so long as the path exists. What exactly didn't work when you tried it? Did it not add the value to the registry at all or was the new value ignored?
It looked like it worked, but when I then opened a command prompt window and typed 'path', the new value ("\\mflo\fds") didn't show up. However, if I tried to add something like "F:\fds" then it would work.
Is there somewhere in the registry it's saved where I could check?