Which is worse getting hit with 220 volts or 480 volts?

All things being equal and in a non-lethal event, 480 would cause more pain. But dead is dead at any voltage.

In the US, both 220 and 480 require at least 2 hot conductors. Someone should never be hit by these voltages because you should never have 2 hot conductors in your hands at the same time.