The solid solution series CexZr(1-x-0.1)Y0.1O2 with various x values was prepared by the citric acid sol-gel method, using cerium and zirconium nitrides as precursors, respectively. The characterization results of the XRD, N2 sorption measurements indicated that the physical properties of the solid solutions were significantly affected by the x values in CexZr(1-x-0.1)Y0.1O2 and the calcination temperatures. These solid solutions can be used as catalyst for the direct synthesis of dimethyl carbonate from CH3OH and CO2. Results indicated that the catalytic activity for DMC synthesis was influenced by the structure of the solid solutions and the x values in CexZr(1-x-0.1)Y0.1O2. The optimized Ce0.5Zr0.4Y0.1O2 with bimodal pore structure exhibited higher catalytic performance to DMC synthesis.