ATX power supplies turn on from a signal loop provided by the motherboard, as opposed to the older AT power supplies that turn on with a mechanical switch. Regardless of the ON/OFF position on the power supply itself, the +3.3V, +5V, +12V, -5V and -12V of the unit will not be live until the unit is "told" to turn on by the motherboard. The fans in the power supply will not spin and only the +5VSB (typically a purple wire) will be live if the power supply is plugged in and in the "ON" position.
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