Abstract: The three-component coupling of methanol, CO₂ and propargyl alcohol to manufacture dimethyl carbonate (DMC) provides a new, thermodynamic favorable and green chemical synthesis route. In this work, to overcome the problems of low DMC yield and slow conversion rate of intermediates, the synergistic catalytic strategy of silver sulfadiazine and superbase is developed to improve the reaction efficiency. The effect of various parameters i.e. catalyst and cocatalyst types, catalyst loading, solvent, temperature, proportion of raw materials, pressure and time on the coupling reactions is investigated in detail. Under the optimal conditions, the selectivity of DMC is 89.5% with the yield of 55.6%. And the effect of alkyne derivative α-monosubstituted propargyl alcohol on the efficiency and selectivity of DMC are also studied. The mechanism study shows that propargyl alcohols with different structures apparently affect the reaction process, and the synergistic catalysis of silver sulfadiazine/1,8-diazabicyclo5.4.0undec-7-ene (DBU) is the reason for the high yield and selectivity of DMC.