CexTi1-xO2 and H3PW12O40/CexTi1-xO2 catalysts were prepared by sol-gel method, and they were applied to the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in a batch reactor. The reaction was carried out in an autoclave reactor at 170oC and 5 MPa. It was found that CexTi1-xO2 exhibited a higher catalytic performance than pure CeO2 and TiO2. The catalytic performance of CexTi1-xO2 was the maximum when x=0.1. It was also revealed that H3PW12O40/CexTi1-xO2 catalysts showed a remarkably enhanced catalytic performance than the corresponding CexTi1-xO2 catalysts. The amount of DMC produced by 15 wt% H3PW12O40/ Ce0.1Ti0.9O2 catalyst was six times higher than that produced by Ce0.1Ti0.9O2 catalyst. It is concluded that both Brönsted acid sites provided by H3PW12O40 and base sites in CexTi1-xO2 played an important role in improving the catalytic performance of H3PW12O40/CexTi1-xO2.