The catalytic properties of CeO 2 catalysts in direct synthesis of dimethyl carbonate (DMC) from CH 3 OH and CO 2 were investigated. The formation rate of DMC over the catalysts calcined at 873K and above was almost proportional to the surface area of catalysts. However, CeO 2 calcined at 673K showed lower activity than expected from the surface area. From the results of catalyst characterization, CeO 2 calcined at 673K contained considerable amount of amorphous phase. In contrast, the ratio of amorphous phase decreased on the catalysts calcined at 873K and above. This suggests that stable crystallite surface is active for the reaction.In the CH 3 OH+C 2 H 5 OH+CO 2 reaction at low temperature, ethyl methyl carbonate (EMC) was formed, and selectivity of EMC formation was comparable to that of DMC. The formation route is discussed by the comparison with transesterification reaction.