Abstract: The experiment uses ethylene carbonate and methanol as raw materials and the LiF/CaO catalyst was prepared by impregnation method. The catalytic activity of LiF/CaO for the synthesis of dimethyl carbonate (DMC) by transesterification of ethylene carbonate (EC) with methanol was studied. The catalysts were characterized by X-ray diffraction, N2 adsorption-desorption and Hammett titration. The results indicated that new phases CaF2 and Li2O were formed when LiF/CaO was calcined. In the case of LiF loading and calcination temperature were 20%(based on mass of CaO) and 500℃, n(Methanol): n(EC) = 10：1, catalyst amount 0.1%(based on mass of EC), reaction temperature 70℃, reaction time 0.5 h. Under these conditions, EC conversion, DMC selectivity and yield were 77.98%, 99.97% and 77.96%, respectively.