The supported n–p coupled semiconductor materials ZnO-TiO 2 /SiO 2 were prepared using the method of modifying the silica surface character. The chemical structure, photoabsorbing behaviors and chemisorbing properties of the catalysts were characterized by IR spectra, Raman spectra, UV–vis reflectance spectra and TPD–MS experiments. It was shown that the ZnOTi bonds have been formed on the surface of ZnO-TiO 2 /SiO 2 catalyst. The addition of ZnO extends the photo absorption range of TiO 2 /SiO 2 sample through the formation of ZnOTi bond. CO 2 and ethane can be chemisorbed on the surface of ZnO-TiO 2 /SiO 2 catalyst and desorbs at 388 and 428K, respectively. Under UV irradiation, CO 2 chemisorption state can undergo discomposing process to form CO at 465K, and a new ethane adsorption state was formed at around 500K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol, acetaldehyde in the temperature range of 393–493K. The presence of ZnO improved the catalytic activity and promoted the formation of hydrocarbon oxygenates. The propanal yield of 75.6μmolh −1 and ethanol yield of 50.9μmolh −1 can be obtained over 5% ZnO-TiO 2 /SiO 2 catalyst at 473K. Reacting temperature has significant effects on the product yields. The temperature of 473K will be preferable for the selective formation of propanal and ethanol.