Series of Alumina supported alkali metal fluoride solid base catalysts were prepared by an impregnation method and applied to the synthesis of glycerol carbonate (GC) via transesterification of glycerol with dimethyl carbonate(DMC). Among these catalysts, KF/γ-Al2O3 could promote the transformation of glycerol into GC more efficiently than other catalysts. The effects of preparation conditions of KF/γ-Al2O3 and reaction conditions on transesterification of glycerol with DMC were investigated. The results proved that the loading amount of KF over KF/γ-Al2O3, calcination temperature and time of catalysts and reaction conditions had significant impacts on the conversion of glycerol and the selectivity of GC. With the molar ratio of DMC to glycerol 3:1, reacted at 80℃ for 1.5h, the conversion of glycerol, selectivity and yield of GC attained 96.1%, 98.1% and 94.3%, respectively, over KF/γ-Al2O3 catalyst with 15wt.% KF loading amount and calcined at 400℃ for 5h.