CO2 is a major greenhouse gas, but also an abundant, cheap and not widely used carbon resource. The direct production of dimethyl carbonate (DMC) from CO2 and methanol is of great significance in the context of “dual carbon goals”. However, the CO2 conversion and DMC yield are too low due to the reaction thermodynamic limitations and inertness of CO2. CeO2-based catalyst is a kind of catalyst with good performance in the direct synthesis of DMC from CO2 and methanol, which has been extensively reported in literature. Therefore, this review focuses on the thermodynamics of the direct synthesis of DMC from CO2 and methanol and the research progress of the reaction mechanism and catalyst studies over CeO2-based catalysts. It also details the methods for controlling the morphology and surface properties of CeO2-based catalysts and the coupling of high-efficiency dehydration agents. It also points out that future work can be carried out in the preparation of CeO2-based catalysts with high specific surface area and high concentration of active sites, in-situ characterization of oxygen vacancy concentration, and the development of new inexpensive and efficient dehydration agents.