A direct liquid fuel cell power generation device comprises a direct liquid fuel cell system and a low-temperature auxiliary starting component. A heat exchanger is arranged at a stack cathode inlet. The heat of a fuel solution at a stack anode outlet is used to heat the air. The heat generated by an electronic load for starting is used to heat a condenser. The heat of a methanol solution at a liquid outlet of a gas-liquid separator is used to preheat high-concentration fuel flowing into a refueling pump. Starting and operation in a low-temperature environment can be realized through auxiliary heating of external power supplies such as the low-temperature auxiliary starting component or an in-vehicle cigarette lighter. Organic micromolecule substances such as methanol and ethanol are used as fuel and are subjected to catalytic combustion in a catalytic combustor.