You can use plaster, ceramics, metal, wood, just about anything that can take the momentary temperature exposure of the heated styrene.
Just to note, if you use regular old modeling clay, your styrene is going to melt into the surface of the material, and it'll be just about impossible to separate it from your mold (it sucks). The easiest way around that is to first vacuum form a thin sheet of styrene over the clay, letting it become a jacket over your original buck. After it cools, trim off your excess, but don't mess with it otherwise. I can't explain the science, but vacuum-formed styrene won't adhere to the styrene outer skin, so that thin jacket ends up working as a mold release. By all means experiment first if you are using a polystyrene variation, but it's worked for me well in the past.