Anhydrous sodium silicate (Na2SiO3) was prepared by the simple calcination of Na2SiO3?9H2O and used as solid base catalyst for the synthesis of dimethyl carbonate (DMC) by transesterification of ethylene carbonate (EC) with CH3OH. Anhydrous Na2SiO3 were characterized by TG-DTA, XRD and Hammett indicator method. Results showed calcination temperature has no significant effect on the basic strength, total basicity and catalytic activity of anhydrous Na2SiO3. When the calcination temperature was 200oC, the basic strength (Ho) of catalyst (Na2SiO3-200) was in the range of 12.2?15.0, and its total basicity was about 10.9 mmol/g. Effects of raw material ratio, temperature and reaction time on the synthesis of DMC were also investigated using Na2SiO3-200 as catalyst. The optimal molar ratio of CH3OH to EC was 10: 1, and the conversion of EC could reach to 89% with 88% DMC yield at 65oC within 2 h. Na2SiO3-200 could effectively promote the reaction even at room temperature. In addition, the catalytic activity of Na2SiO3-200 has no remarkable decrease after 4 runs.