You can.. I've done it with several devices including a Fibaro Key Fob.
The hub can get a little fussy after you pair it using the secondary controller. Sometimes the device will not show up except on the Z-Wave details page. A reboot after repair etc usually does the trick but not sure what combination of "repair/refresh/discover/reboot" actually works. Also I don't think you have to pull the power on the hub for this one.
Note: It pairs unsecured by default at least that's been my experience. I used a Z-Stick+ but am pretty sure any stick compatible with the PC Controller will work.
edit: leaving this post in case someone else finds it useful!
