The hydrogenation of carbon dioxide (CO 2 ) to produce chemicals and transportation liquid fuels in huge demand via heterogeneous thermochemical catalysis achieved using renewable energy has received increasing attention, and substantial advances have been made in this research field in recent years. In this study, we summarize our progress in the rational design and construction of highly efficient catalysts for CO 2 hydrogenation to methanol, lower olefins, aromatics, and gasoline- and jet fuel-range hydrocarbons. The structure-performance relationship, nature of the active sites, and mechanism of the reactions occurring over these catalysts are explored by combining computational and experimental evidence. The results of this study will promote further fundamental studies and industrial applications of heterogeneous catalysts for CO 2 hydrogenation to produce bulk chemicals and liquid fuels. The hydrogenation of CO 2 to chemicals and fuels has a distinct CO 2 emission reduction effect. In this study, the catalyst design, selectivity regulation, structure-performance relationship, and reaction mechanism are discussed in detail.