An organocatalytic protocol for the synthesis of dimethyl carbonate has been developed. Under the catalysis of 5 mol% N-heterocyclic carbenes, ethylene carbonate undergoes transesterification reaction with methanol under very mild reaction conditions, producing dimethyl carbonate with high efficiency. Furthermore, this N-heterocyclic carbene promoted transesterification can be scaled-up easily without lose of the conversion of dimethyl carbonate.