Glycerol carbonate (GC) was synthesized via transesterification of glycerol with dimethyl carbonate under mild conditions over a series of base zeolites. It was found that the NaY zeolite exhibited a higher selectivity for GC (100%) than heterogeneous bases (such as CaO and SrO) or homogeneous catalysts (such as NaOH and K2CO3). Further experiments over different base zeolites disclosed that this trans-esterification reaction depended strongly on catalyst structure. Base zeolites with small pore diameter such as 3A,4A, and NaZSM-5 were inactive, while NaY and Naβwith larger pore diameter exhibited excellent GC yields under mild conditions.