A series of CuO-V2O5/TiO2 catalysts with different Cu contents were prepared by wet impregnation method and used in selective catalytic reduction of NO with NH3. The aim of this design was to improve the low-temperature selective catalytic reduction (SCR) performance and broaden the temperature window compared to V2O5/TiO2 and CuO/TiO2. It was found that the NO conversion over Cu-V/Ti was greatly improved with V2O5/TiO2 and CuO/TiO2. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H-2-TPR), temperature programmed desorption of ammonia or nitric oxide (NH3-TPD and NO-TPD). The results indicated that copper species had a good interaction with TiO2, vanadium species interacted with TiO2 by copper species, thereby generating more V4+. This had led to the increasing of chemisorb oxygen, better reduction property, more surface acid sites, and improvement of NH3 and NO adsorption capacity, all of these resulting in better NH3-SCR performance of 10Cu-V/Ti catalysts. Furthermore, the catalyst showed a good H2O and SO2 resistance at activation temperature.