The chemical conversion of CO2is considered as one of the effective measures to reduce carbon emission, where breakthroughs have been made in the thermo-catalytic hydrogenation of CO2to ethanol in recent years. However, the synthesis of ethanol from CO2still suffers from some problems such as low ethanol yield and abundant by-products. In this paper, the research progress made in the thermo-catalytic hydrogenation of CO2to ethanol was reviewed. The performance of various catalysts with zeolites, metal oxides, perovskites, silica, organic frameworks and carbon-based materials as the support was evaluated and the synergistic effect of different metals on the CO2conversion and the intervention of various active species on the reaction were analyzed. Accordingly, the catalyst systems that can effectively promote the adsorption and activation of CO2and the coupling of C–C bond were summarized. Finally, the appropriate conditions as well as possible reaction mechanism for the CO2hydrogenation to ethanol were proposed. The insight shown in this paper should be beneficial to designing efficient catalysts, optimizing the reaction conditions and understanding the mechanism of CO2hydrogenation to ethanol in the future.