The synthesis of dimethyl carbonate (DMC) from urea and methanol was investigated, to explore the catalysts and reaction conditions. Among the catalysts, ZnO showed the highest catalytic activity toward DMC synthesis. Based on the experimental investigation, the reaction conditions over ZnO for a batch process were optimized, and the highest DMC yield attained (based on urea) was similar to 30%, because of the presence of side reactions. In addition, the reusability test indicated that ZnO had high stability.