USB and PS/2 both have 0V and +5V power lines, so initial power up is no problem.
PS/2 has two open collector data lines, normally at +5V unless pulled low by a transmission.
USB has a differential signal carried over the two data lines, one will be near 0V, the other at 2.8 - 3.6V.
Monitoring the two data lines for a short while should reveal what bus is in use.