Abstract: A complex catalyst system，SO42－/ZrO2-TiO2 was prepared and used in the reaction for the synthesis of glycerol triacetate from glycerol and acetic acid and the process of alcohol distillation recovery. By improving the process，avoiding the use of toxic water-taking agent，the synthesis process of glycerol triacetate was made more safe，economical and environmentally friendly. The optimal conditions for the catalyst and glycerol triacetate preparation were as follows，the concentration of sulfuric acid impregnation solution，0.5～0.55mol.L－1; calcinations temperature，550~600℃; catalyst dosage，2.5%～3.0% (the mass fraction of the total material); ratio of glycerol and acetic acid，nglyceroal：nacetic acid=1∶5.5; reaction temperature，130℃，reflux reaction time about 3 h; the yield of the product 93.6%; catalyst could be reused six times，and catalyst regeneration was easy.