Enhanced performance of Ce doping on the catalytic activity of V2O5-WO3/TiO2 catalysts and its resistance properties to Na poisoning have been investigated in the research. Different Na species (NaCl and Na2O) were deposited on CeO2-V2O(5)-WO3/TiO2 catalysts by impregnation method. The results presented that CeO2-V2O5WO3/Tio(2) catalysts exhibited a higher NH3-SCR activity and better Na resistance than the V2O5-WO3/TiO2 catalyst, and its poisoning resistance to Na2O is more superior than to NaCl, caused by more acid sites over the 10%CeO2-V2O5-WO3/TiO2 (Ce10VWTi) catalyst, which indicated that the poisoning resistance of Na2O on Ce10VWTi catalysts is higher than that of NaCl. Combined with the characterization results, the dopant of Ce could enhance the surface chemisorbed oxygen on the Na poisoning V2O5-WO3/TiO2 catalysts, facilitate the redox cycle, and increase the intensity of acid sites due to the newly formed Bronsted acid sites stemmed from Ce3+ - NH4+, thereby promoting catalytic activity and Na poisoning resistance.