Electrochemical carbonylation of methanol to dimethyl carbonate (DMC) at room temperature and atmospheric pressure in a self-fabricated two-compartment electrolytic cell was achieved using CuCl2-2,2'-bipyridyl as catalyst. The reaction mechanism was analyzed, and the influence factors such as supporting electrolyte, anode potential, and concentration of supporting electrolyte and CuCl2-2,2'-bipyridyl were evaluated. The proper conditions for the electrosynthesis of DMC were obtained, in which the content of DMC was 0.1279%, the current efficiency of DMC was 76.4%, and the amount of DMC was 0.3161 mmol. In the distilled anolyte after reaction no other species but CH3OH and DMC were found via gas chromatography.