We have just started to use Git, Github and Git TFS. We are in the process of moving from TFS to Git, and Git TFS is working great! We still need TFS around for a short while longer while we move our build scripts to read from Github instead of TFS, but until that day comes we have to copy the changes back in to TFS.
No, Git TFS isn't strictly a one user system, but I guess it comes down to how you chose to use it.
In our system one developer checks in the results from a dedicated branch on Git in to our TFS master branch using Git TFS when we need to copy the new changes back in to TFS (to trigger the build scripts). However, up until that point we just use Git and Github for all work and code collaboration.
As has been mentioned, the 'Git TFS bootstrap' command can come in useful for the developers that didn't perform the initial checkout of code from TFS since this command copies the necessary TFS information to the local .git/config file pointing them at the correct TFS branch. If they ever want to pull or checkin then they will need this first along with Git TFS installed on their local machines.