WO3/TiO2 samples were prepared by sol-gel process and characterized by means of XRD, LRS, TEM, DRS, BET, XPS, It has been shown that the mean crystal diameter and mean particle diameter of W0\O-3/TiO2 samples decreased while the percent of anatase and specific surface area increased owing to the doping of WO3, New LRS peaks presented at 797, 967 and 969 cm(-1), respectively, when the concentration of doped WO3 was 2%, 5% and 8%, The reflectance percentate of WO3/TiO2 samples was less than that of pure TiO2 in the range of 380-460nm. The XPS fitting analyses showed that there were W6+,W5+,W4+ and Ti4+, Ti3+ in the lattice of WO3/TiO2, Being a model reaction, the photo-catalytic degradation of methylene blue was investigated in TiO2 and WO3/TiO2 nanopowder suspension irradiated by high-pressure mercury lamp. As a result, the addition of WO3 to TiO2 greatly enhanced its photo-catalytic behavior, and the optimum concentration of WO3 in TiO2 was 2% (molar percent). Moreover, the relationship between photo-activity and the physical and chemical properties of the samples have been discussed.