The PG rail is asserted to 5v when the PSU is operating within normal parameters. It is typically asserted 100-500ms after Power_On has been held low and the PSU has turned on.
In the case of overload or overheat or overvoltage, the PSU will de-assert PG and the voltage will drop to 0v on that line, or the PSU switches off.
The Motherboard responds to PG like so - When PG is asserted at turn-on, the Motherboard starts the POST and bootup routine. If PG is de-asserted when the computer is on then the motherboard will reset the system, or turn itself off.