Electrochemical oxidative carbonylation of methanol with CO to dimethyl carbonate from heterogeneous electrocatalyst was studied at normal temperature and pressure. For the purpose of decrease the crystalline size and the agglomerative force of metal-organic framework (MOF), this paper first introduced graphite oxide (GO) into MOF/GO hybrid material with enhanced electrocatalytic performance and the stability of electrocatalyst for the dimethyl carbonate (DMC) synthesis. The introduction of GO is important to build the hybrid materials with synergistic properties. The composite materials and its parent materials were characterized using X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and the electrochemical property of the samples was measured. The results show that the MOF/GO was active for the electrolytic reaction and could be reused at least five times. A plausible Cu(II)/Cu(I) electrocatalytic cycle mechanism was proposed.