Cerium dioxide (CeO2) was pretreated with reduction and reoxidation under different conditions in order to elucidate the role of surface Ce4+and oxygen vacancies in the catalytic activity for direct synthesis of dimethyl carbonate (DMC) from CO2and methanol. The corresponding catalysts were comprehensively characterized using N2physisorption, XRD, TEM, XPS, TPD, and CO2-FTIR. The results indicated that reduction treatment promotes the conversion of Ce4+to Ce3+and improves the concentration of surface oxygen vacancies, while reoxidation treatment facilitates the conversion of Ce3+to Ce4+and decreases the concentration of surface oxygen vacancies. The catalytic activity was linear with the number of moderate acidic/basic sites. The surface Ce4+rather than oxygen vacancies, as Lewis acid sites, promoted the adsorption of CO2and the formation of active bidentate carbonates. The number of moderate basic sites and the catalytic activity were positively correlated with the surface concentration of Ce4+but negatively correlated with the surface concentration of oxygen vacancies. The surface Ce4+and lattice oxygen were active Lewis acid and base sites respectively for CeO2catalyst, while surface oxygen vacancy and lattice oxygen were active Lewis acid and base sites, respectively, for metal-doped CeO2catalysts. This may result from the different natures of oxygen vacancies in CeO2and metal-doped CeO2catalysts.