Catalytic carbon dioxide (CO2) hydrogenation is a potential route for producing sustainable fuels and chemicals, but existing catalysts need improvement. In particular, identifying active sites and understanding the interaction between components and the dynamic behavior of the participant species remain unclear. This fundamental knowledge is essential for the design of more efficient and stable catalysts. Because the nature of the active site (metal, oxide, carbide) is the main factor that determines the catalytic activity of the catalysts, this Review focuses on various types of heterogeneous catalysts that have been recently reported in the literature as efficient for CO2 conversion to C1 [carbon monoxide (CO), methanol (CH3OH), methane (CH4)], and higher hydrocarbons. We focus on establishing key connections between active-site structures and selectivity, regardless of catalyst composition.