In this study, UiO-66 @CeO₂ composites was prepared by loading CeO₂ nanoparticles on the surface of UiO-66 using precipitation method, and the effect of CeO₂ loading on the catalytic direct reaction of CO₂ and methanol into dimethyl carbonate (DMC) was investigated. XRD, N₂ adsorption-desorption, FT-IR, XPS, SEM and TEM were used to investigate the physical and chemical properties of UiO-66 @CeO₂. The results showed that the framework structure of UiO-66 benefit the high dispersion of CeO₂, while the loading of CeO₂ provided more oxygen vacancies, which promoted the capture and absorb of CO₂, thus promoted the reaction synergistically. Among which, UiO-66 @CeO₂-60 showed best activity, with the highest DMC formation rate of 2.84 mmol·g⁻¹·h⁻¹ (yield: 2.27%) within 4 h of reaction time under the optimum conditions. In addition, the catalyst also showed favorable reusability, maintaining ∼90% of catalytic efficiency with 4 reuse cycles compared the fresh ones.