A series of Ce/SBA-15 catalysts with different degrees of hydrophobicities were prepared via a post-grafting method and used for the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. The Ce/SBA-15-6 catalyst exhibited the highest DMC yield of 0.2%, which was close to the equilibrium value under the reaction conditions of 130 °C, 12 h and 12 MPa. The catalysts were characterized via XRD, BET, FT-IR, solid-state 29Si MAS NMR, CA, TEM, XPS and NH3/CO2-TPD; the results indicated that the hydrophobicity of the catalysts facilitated the creation of oxygen vacancies, which could act as Lewis acids to activate methanol. Higher amounts of moderate acid sites led to higher yields of DMC. In addition, the hydrophobicity of the catalysts could also reduce the adsorbed water on their surface and increase the DMC yield while shortening the reaction time.