Poisoning by Na is one of the major issues for the commercial SCR catalyst. In this study, Ce(SO4)2 was added to the catalyst system of V2O5/TiO2 to enhance its resistance to Na poisoning. The results show that Ce(SO4)2 addition will increase the NOx conversion of V2O5/TiO2 catalyst at medium temperatures of 330°C–450°C. After doping by sodium with a molar ratio of Na/V = 1/1, the V2O5-Ce(SO4)2/TiO2 catalyst still show excellent DeNOx efficiency, about 40% higher than commercial V2O5-WO3/TiO2 catalyst. The fresh and Na poisoned catalysts were characterized by XRD, SEM, NH3-TPD and H2-TPR. The results show that the Ce(SO4)2 addition will remarkably strengthen the surface acidity and redox ability of V2O5/TiO2 catalyst. The TPD results also show that the V2O5-Ce(SO4)2/TiO2 catalyst can maintain its surface acidity after Na doping, while the acidity of V2O5-WO3/TiO2 catalyst will dramatically decrease. The redox ability of the catalyst can also be better kept when Ce(SO4)2 is added into the catalyst system.