As of the most recent Steam Client Beta steam now supports an experimental VR mode. If you own an Oculus Rift dev kit you can try it out by starting Steam with "-vr" on the command line. Then press the Big Picture button to enter Big Picture + VR mode.

The first time you run you may need to do the following:
1) Run Steam in the desktop client without the -vr option
2) Find "SteamVR" under "Tools" in your library. (If you don't have it installed, install it.)
3) Bring up properties on SteamVR and opt-in to the "Beta Update" beta. Let the update download.
4) Quit the Steam Client again and start it with -vr

Please use this forum to provide feedback on VR mode.