CexZr1-xO2 catalysts with different Ce/Zr mole ratios were prepared by the sol-gel method and used for the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. Among a series of CexZr1-xO2 catalysts, Ce0.8Zr02O2 catalyst exhibited the highest catalytic activity. Characterization results demonstrated that doping Zr into CeO2 can lead to the formation of the Ce-O-Zr solid solution, which would strengthen the interaction between ZrO2 and CeO2. Ce0.8Zr02O2 catalyst possessed the highest concentration of oxygen vacancy sites, thus exhibiting the highest activity for the direct synthesis of DMC. Display omitted •CeO2-ZrO2 solid solution catalyst was prepared by the sol-gel method.•Strong interaction between ZrO2 and CeO2 existed over CeO2-ZrO2 catalyst.•Ce0.8Zr02O2 exhibited the highest activity for DMC synthesis from CO2 and methanol.•Both the oxygen vacancy and particle size are important for the activity in DMC synthesis.