Thermocatalytic hydrogenation of carbon dioxide (CO2) offers a promising approach to achieving net negative emissions by transforming CO2 into value‐added products like carbon monoxide (CO), methane (CH4), and methanol (MeOH). The design of catalysts plays a pivotal role in CO2 hydrogenation, particularly in configuring effective catalytic sites. In this review, we first introduce important characterization techniques for CO2 hydrogenation catalysts and discuss the identification of the catalytic sites in CO2 hydrogenation catalysts, including those for hydrogen (H2) activation, CO2 adsorption/activation, and others. We then delve into reaction systems that utilize single and/or multiple catalytic sites for processes such as the reverse water‐gas shift (RWGS), CO2 methanation, and MeOH synthesis, highlighting how the multiple‐site configurations can significantly influence catalytic activity and selectivity. Catalytic Sites Contiguity (CSC) is finally introduced to emphasize the critical relationship between the spatial arrangement of catalytic sites and the efficiency of reactant activation and conversion. Specific examples in MeOH synthesis from CO2 hydrogenation are presented to illustrate the impact of CSC on catalytic performance, offering insights into the potential for optimizing CO2 hydrogenation catalysts.