The catalyst (HPW/APTES-SiO2) of heteropoly acid supported on acid activated and silanizing silica (APTES-SiO2) by 3-aminopropyl-triethoxysilane (APTES) was prepared via chemical bonding. The properties of the catalyst was characterized by infrared spectroscopy, X-ray diffraction, Brunauer–Emmett–Teller (BET) specific area measurement and thermogravimetric analysis（TG-DTA）.The catalytic activity of the catalyst was determined by the condensation of cyclohexanone with glycerol. The highest conversion of cyclohexanone and the selectivity of 1,4-dioxasp iro[4,5] decane-2-methanol reached 92.7% and 97. 8%, respectively, by using HPW/APTES-SiO2 as the catalyst under the optimum reaction conditions .The recycling tests show that the catalyst can be easily separated from the reaction system and to be reused many times.