Basically as long as DirectInput can make use of a game controller that's connected, yes. All you have to do is select it in the "Game & I/O Ports" section, and then configure it in the "Input" section.
Just as a hint, if you need to configure it to act like a CD32 pad, here is how the layout is:
Rewind FastFoward
Up Green Yellow
Left Right
Down Play/Puse Red Blue
I hope that helps out for when you configure the gamepad.