Excessive carbon dioxide (CO2) emissions are one of the main causes of the greenhouse effect. Thermal catalytic reverse water gas shift (RWGS) reaction, which is a pre reaction for Fischer–Tropsch synthesis, is considered an effective way to convert CO2 and synthesize high value‐added chemicals in industry. However, traditional thermal catalysis requires a large amount of fossil fuels to drive reactions, which cannot achieve the true goal of carbon neutrality. Photothermal catalysis, as a novel conversion pathway, can achieve efficient CO2 conversion while significantly improving solar energy utilization. This review provides a detailed introduction of CO2 and H2 adsorption/activation and reaction pathways in thermal catalysis, as well as the catalytic mechanisms of thermal and chemical effects in photothermal catalytic RWGS to supply readers valuable insights on the mechanism of photothermal catalytic RWGS reaction and provide a reference for better catalyst design.