The environmental friendly catalyst, H₄SiW₁₂O₄₀/TiO₂-SiO₂ was prepared by the impregnation method. The synthesis of cyclohexanone glycol ketal was as the probe reaction and investigated the different influences on the catalytic activity of H₄SiW₁₂O₄₀/TiO₂-SiO₂ by the quality of the carrier TiO₂-SiO₂ ratio, load of heteropoly acid, catalyst preparation conditions of the activation time and the calcination temperature, etc. The results showed the best condition for the preparation of the catalyst is the mass ratio of TiO₂ and SiO₂ is 1: 5, the load ratio of H₄SiW₁₂O₄₀ is 10 %, calcination temperature is 300 oC and the roasting time is 3.0 h. Under the condition of the molar ratio of aldehydes (ketones) and glycol (1,2-propanediol) is 1: 1.6, the mass percent of the catalyst is 1.4 %, and the reaction time of 70 min, the yields of eight kinds acetal (ketal) are 71.6 %~ 90.5 %.