I essentially followed this to get it to work.
How to use PS3 Controller on Windows 7 and Windows 8 - Windows 7 - WinMatrix
Great, but that guide specifically says it only works through USB?? You said you got it working via Bluetooth?
I essentially followed this to get it to work.
How to use PS3 Controller on Windows 7 and Windows 8 - Windows 7 - WinMatrix
I can confirm that ePSXe and several PS1 games work without a hitch. I created the ISO from the original games to test, and so far Metal Gear and Vagrant Story play great on it. I have the PS3 controller setup via Bluetooth.
I have installed the newest version of PCSX as well, but I have to create an ISO of a game to test it, so far the emulator runs without issue, though.
I now have NES, SNES, PSX and PS2 setup. This is turning out to be a sweet on the go vintage gaming machine!