CO2 hydrogenation is one of the most promising processes in response to energy crisis and greenhouse gas emission. There is, however, still a lack of a highly efficient and sustainable catalyst for this reaction. In this study, a novel low-cost core-shell structured CuIn@SiO2 catalyst is prepared by a solvothermal method and used for catalyzing CO2 hydrogenation to methanol. A significant interaction exists between Cu and In, promoting Cu dispersion and reducibility, Cu2In alloy and oxygen vacancy formation. Moreover, plenty of interfacial sites are formed between Cu2In and In2O3, which further enhances CO2 adsorption and activation. CuIn@SiO2, therefore, shows not only a satisfactory catalytic stability due to core-shell formation but also an excellent catalytic performance. 9.8% CO2 conversion, 78.1% CH3OH selectivity, and 13.7 mmol(CH3OH.)h(gcat)(-1)(-1) CH3OH space-time yield are obtained at the space velocity of 20,000 mL.g(cat)(-1.)h(-1). CuIn@SiO2 possesses a great potential as catalyst for CO2 hydrogenation in a moderate condition in industry. (c) 2018 American Institute of Chemical Engineers