The invention relates to a zero carbon poly-generation system and method coupling thermal power generation with CO2 conversion. According to the system, a thermal power generation system can be utilized for generating electric energy; compared with a traditional thermal power generation system, CO2 generated in a boiler is converted to generate CO through a CO2 conversion system, CO enters a gas turbine for acting to generate electric energy, and therefore under the condition of the same generating capacity, coal consumption of the system can be reduced, and energy can be effectively saved; and by means of application of various gas purification devices, it can be guaranteed that the reaction efficiency reaches the maximum, and the energy utilization rate is increased. Part of CO generated through the CO2 conversion system can generate needed chemical products through Fischer-Tropsch synthesis, zero carbon emission of the whole system can be achieved, energy saving and environment friendliness can be achieved, and the energy utilization rate can be increased. In the whole zero carbon poly-generation system, all systems are connected closely, no poisonous gas such as CO is discharged, and the phenomenon of gas poisoning of operators cannot be caused; and the automation degree is high, the number of the operators can be reduced, and the cost can be reduced.