A V2O5/N-doped TiO2 catalyst has been developed by partly substituting the lattice oxygen of TiO2 support with nitrogen, which showed a remarkable increase in activity for the reduction of NO with NH3 at low temperature. The catalyst was characterized by Brunauer–Emmett–Teller (BET), transmission electron microscope (TEM), photoluminescence (PL), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR). The results demonstrated that N doping cannot noticeably change the microscopic features but dramatically enhanced the formation of surface oxygen vacancies, which can play a vital role in the formation of superoxide ions to improve the SCR activity. The catalyst with [N]/[Ti]=1.0×10−2 showed the highest NO removal efficiency in the SCR reaction at low temperature. Furthermore, the V1TiN1.0 catalyst showed better resistance to SO2 and H2O during the SCR of NO.