Herein the synthesis of dimethyl carbonate (DMC) from the direct alcoholysis of urea in supercritical methanol system was proposed. The effects of different reaction conditions, such as reaction temperature, reaction time, the molar ratio of methanol/urea, reaction pressure, the volume of reaction solution, the treating reactor and the amount of water on DMC yield were systematically investigated. The experimental results indicated that the optimal reaction conditions were reaction temperature of 538 K, time of 2 h, the molar ratio of methanol/urea of 14, and the reactor loading of 285 mu L, respectively. And the DMC yield was 98% under the optimal reaction condition. (C) 2013 Elsevier B.V. All rights reserved.