Electrocatalytic activation and conversion of methanol and CO 2 to dimethyl carbonate with graphite and platinum electrodes in the dialkylimidazolium ionic liquid-methanol system was conducted under ambient conditions. Among the ionic liquids screened, 1-benzyl-3-methylimidazolium chloride (BzmimCl) exhibited effective performance as a supporting electrolyte. In the process of the electrolysis, dimethyl carbonate was effectively synthesized in the absence of any other additives. Based on the electrochemical activation of the methanol on the electrode, insertion of CO 2 , CH 3 OH participating in the reaction, the electrochemical reaction mechanism proposed here is very different from those previously reported.