Catalytic reduction of CO2 to valuable products is an attractive route for CO2 recycling. CeO2-supported Cu catalysts have shown high activity and selectivity for the hydrogenation of CO2 to CO. To uncover the origin of their high performance, we prepared a practical and well-defined model of Cu/CeO2–x catalysts with Cu nanoparticles dispersed on a CeO2–x support. We studied the structure and catalytic activity of the practical catalyst and the evolution of the active phase and surface intermediates using near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) over the model catalyst under CO2 hydrogenation conditions. For both model and practical catalysts, metallic copper and partially reduced ceria with oxygen vacancies were found to be active sites for the reduction of CO2 to CO. Over the model catalyst, partial covering of Cu by CeO2–x and diffusion of Cu into CeO2–x was observed, suggesting that a strong interaction between Cu and CeO2–x was favored during CO2 hydrogenation. The surface analysis results indicated that the CO2 hydrogenation proceeded through the following steps: activation of CO2 in the form of carbonate on the surface of CeO2–x, hydrogenation of carbonate to formate on the surface of Cu by the dissociated H2, and conversion of formate to CO. This work provides direct experimental evidence on the surface properties of Cu and ceria during the RWGS reaction and the activation and hydrogenation processes of CO2 over the Cu/CeO2–x surface for a high RWGS catalytic performance.