Dimethyl carbonate (DMC) is one of the important green chemicals, and the oxidative carbonylation of methanol is thermodynamically beneficial, which has been regarded as the most promising route for DMC synthesis. Herein, this review highlights recent developments in various catalysts for synthesizing DMC via oxidative carbonylation of methanol. In particular, the preparation methods, structural optimization as well as catalytic performance regulation for the most studied carbon supported copper catalysts was summarized and discussed in a comprehensive perspective. In addition, the main product and by‐products formation pathways, and reaction mechanisms of methanol oxycarbonylation were elaborated thoroughly. Finally, the current status of industrilization for the DMC synthesis via methanol oxycarbonylation was summarized. This work provided a theoretical basis and practical guidance for the oxycarbonylation of methanol, which is helpful to develop highly efficient and stable catalysts so as to accelerate and update the DMC systhesis technology.