In this work, the protic ionic liquid [DBUH][Im] (1,8-diazabicyclo[5.4.0]-7-undeceniumimidazolide) was developed as an efficient catalyst for the transesterification of ethylene carbonate with methanol to produce dimethyl carbonate. At 70 ° C, up to 97％ conversion of ethylene carbonate and 91％ yield of dimethyl carbonate were obtained with 1 mol％[DBUH][Im] (relative to ethylene carbonate) as catalyst in 2 h. Even at room temperature, the conversion of ethylene carbonate can reach 94％ and the yield of dimethyl carbonate can approach 81％ for 6 h. Catalytic mechanism investigation showed the high catalytic efficiency of this ionic liquid results from the synergistic activation effect, wherein the cation can activate ethylene carbonate and the anion can activate methanol through hydrogen bond formation. Although the reusability of the ionic liquid need to be further improved, high efficiency and commercial availability of [DBUH][Im] render it a promising catalyst for the preparation of dimethyl carbonate.