Highly dispersed V2O5/SiO2(CVD catalyst) was prepared by the reaction of vaporized VO(OPri)(3) with silica at 293 K, whose process was followed by an IR technique. The rate of propylene photooxidation increased with an increase in V2O5 loading for CVD catalysts, but leveled off for impregnated ones. The CVD catalysts were characterized by XAFS and photoluminescence spectroscopy.