High surface area ZrO₂–KOH sample was prepared and used the catalyst for the synthesis of glycerol carbonate (GC) from dimethyl carbonate (DMC) and glycerol. The structure properties of ZrO₂–KOH were characterized by XRD, BET, CO₂-TPD, XPS, and ICP-OES. It was found that the strong basicity of ZrO₂–KOH might be attributed to the oxygen vacancies as well as the big surface area. Experiments were developed to evaluate the effects of catalysis loading, proportion of reactants, temperature and reaction time on the conversion of glycerol to GC. The consequences showed that ZrO₂–KOH was a highly efficient basic catalyst for synthesis of GC from glycerol. The catalytic performance of ZrO₂–KOH is much better than that of ZrO₂–KOH–CP, ZrO₂–NH₄OH, and some reported heterogeneous catalysts. And the higher performance of ZrO₂–KOH was ascribed to the strong basicity. 99.43% conversion was obtained in a particular situation of catalyst/glycerol weight ratio of 3 wt%, DMC/glycerol molar ratio of 3:1, reaction temperature of 80 °C, and reaction time of 2 h. The plausible reaction mechanism for the transesterification on the strong basic active sites was discussed.