The burning of large amounts of fossil fuels has led to a rise in greenhouse gas emissions and global warming. The world has proposed a global agreement to reduce CO2 emissions, and China has proposed the goal of “carbon peaking and carbon neutrality”. CO2 capture and conversion to liquid fuels and chemicals are one of the effective carbon reduction measures under the carbon peaking and carbon neutrality targets, which not only can realize the resource utilization of CO2, but also alleviate the national energy security problem. In this paper, we analyze the CO2 to methanol process coupling green hydrogen, which is based on four different CO2 capture technologies, taking CO2 capture from flue gas of coal-fired power generation and CO2 to methanol as the research objects. Rigorous steady-state modeling and simulation of the CO2-to-methanol process with four different CO2 capture technologies are carried out, and compare the technical-economic performance of the CO2-to-methanol process under different cases of CO2 capture technologies. The results show that the energy consumption per unit of methanol is 7.81, 5.48, 5.91 and 4.66 GJ/t CH3OH for the MEA case, PCS case, DMC case and GMS case, respectively. And the GMS case has the lowest energy consumption, followed by the PCS case, but with the development of more efficient phase change solvents, the energy consumption will be reduced to 2.29—2.58 GJ/ t CH3OH for the PCS case. The total production costs of the four cases are 4314, 4204, 4279 and 4367 CNY/ t CH3OH, respectively, and the PCS case has the lowest cost and is more economically competitive. The comprehensive analysis shows that the PCS case has the best performance and can be used as the best carbon capture technology for coal-fired power plants, providing directions for efficient CO2 synthesis of fuel chemicals to alleviate fossil fuel shortage and environmental pollution problems.