The Chevy Volt uses grid electricity stored in the battery to drive Electric Miles. Hold Mode can be used to "save" some grid power for later use. Once you fully deplete the battery, you won’t have any more grid power in the battery until you plug into the wall. No grid power, no Hold Mode.
Once you fully deplete the battery, you can switch to Mountain Mode to use its "feature" that will rapidly recharge your depleted battery to the MM-maintained state of charge (~2 bars for a Gen 2, ~4 bars for a Gen 1 Volt) using a small amount of extra gas (less than 0.4 gallons for a Gen 1). MM is designed to maintain a larger Extended Range Mode buffer of battery power that can be "borrowed" if needed when driving in high power demand conditions (such as when driving fast up a mountain road).
Once MM has recharged the battery to the MM-maintained SOC, the car operates much like Hold Mode, keeping the SOC at that point. If you switch to MM as you start driving or any time before the battery SOC has dropped to the MM-maintained level, the car will remain in Electric Mode until that MM-maintained battery state of charge level has been reached. It will then switch to MM and use no more gas than it would in Hold Mode.
Note that if you use MM to recharge a depleted battery while driving, this MM-recharged battery power is NOT "grid" power. If you then switch back to Normal mode, the motor will use the MM-recharged battery power to propel the car, but the distances will register as Gas Miles (you used gas to MM-recharge the battery).
If you recharge your depleted battery using MM there is really no reason to switch to Hold Mode. MM is, in effect, a "hold" mode at that specific state of charge level.
If your goal is to artificially inflate your ev mileage and deflate your MPGcs gas mileage numbers by using MM-recharged battery power to drive Electric Miles, you can do that by turning the car off and back on again after MM has recharged the depleted battery.
When the car is restarted, the computer will recognize the battery state of charge is above the normal switch to gas level and will count the use of that battery power as Electric Miles. I suppose you could now use Hold Mode to "save" this power for later use.
You will note the kWh Used on the energy usage screen will not increase as you use this power (it is not grid power). The MM-recharged battery-powered miles will add to the total Electric Miles without using any grid power and reduce the total Gas Miles without reducing the Gas Used numbers.