Depends on the pedal and the application.
A volume pedal that has audio going through it can't be used as an expression pedal on synths (or whatever).
On keyboards, the expression pedal input can be programmed to be used as a volume pedal or for filter sweeps or whatever (depending on the synth). This has to be an expression pedal type, ie. one that doesn't pass audio through, a pedal with one cord attached to it that goes into an expression pedal input.
Oh, volume is an expression tool, in a way. What are you trying to do?