As long as you can direct the MIDI output to an external device, it should work fine. I remember playing FF7 with the audio coming out of my Yamaha keyboard via MIDI cable.

Personally, I'd build a DOS rig with an LAPC1 card before I bothered doing it on a modern PC. Less clutter, and probably easier to use.

I'm happy with my AWE64, though. Some people like the awesome sampled sounds of the Rolands, but there's something odd to me about DOS games sounding like that. What games are you planning on playing with this?