In the synthesis routes of dimethyl carbonate,one-pot transesterification has the advantages of easy process,low investment and benign to environment.Using the mixture of KI and K_2CO_3(mass ratio of KI/K_2CO_3=1∶3~5∶3) as the catalyst,dimethyl carbonate selectivity can reach up to 73% at 100% ethylene oxide conversion at the appropriate reaction conditions.