A new environmental friendly catalyst, H3PW12O40/SiO2 was prepared with the sol-gel method, and characterized by FT-IR and XRD. Cyclohexanone ethylene ketal was synthesized from cyclohexanone and ethylene glycol using H3PW12O40/SiO2 as the catalyst. The influence factors on the yield of cyclohexanone ethylene ketal were also discussed. The optimum conditions were indentified: molar ratio of cyclohexanone and ethylene glycol is 1:1.3, mass fraction of catalyst to reactants is 1.2%, cyclohexane dosage is 3 mL and reaction time is 45 minutes. The yield of cyclohexanone ethylene ketal can reach 89.7% under the optimum conditions.