I’m currently dealing with the RF stuff as part of my node.js library rewrite, and as far as I can tell (I don’t own the RF switches, just the AllOne), there is no RF learn mode. It seems like the 433mhz is solely to control their RF switches, and is only one way. The way I think it works, is like so:
You install the RF switch and set up the AllOne with your phone. You press and hold a button on the RF switch until it beeps. You go into WiWo (the app for the AllOne) and add a new light or switch device to your AllOne. This device is NOT stored on the AllOne — it’s stored on your phone. You go into the new switch you created in the app and press a button. The AllOne sends an RF message to the listening RF switch. Part of that message is an “RF ID” which ties that button you created in WiWo, to the RF switch.
I don’t know how this RF ID is created (I’m still trying to work that out) so I don’t know if you can create another switch in the WiWo app on another phone and control it. I highly doubt it, because part of the RF ID (as I understand it) changes each time you create a switch, but part of it stays the same.
So TL;DR: No, this thing doesn’t have an RF learn mode and the RF is pretty much only good for their RF switches. Try the Broadlink RM2 Pro which definitely has RF learning mode (I hooked my doorbell up to it and rang it via the app, so it definitely learns and plays back!)