Three kinds of Ce-based catalysts (CePO₄, CeVO₄, Ce₂(SO₄)₃) were synthesized and used for the selective catalytic reduction (SCR) of NO by NH₃. NH₃-SCR performances were conducted in the temperature range of 80 to 400 °C. The catalytic efficiencies of the three catalysts are as follow: CePO₄ > CeVO₄ > Ce₂(SO₄)₃, which is in agreement with their abilities of NH₃ adsorption capacities. The highest NO conversion rate of CePO₄ could reach about 95%, and the catalyst had more than 90% NO conversion rate between 260 and 320 °C. The effect of PO₄^3–, VO₄^3– and SO₄^2– on NH₃-SCR performances of Ce-based catalysts was systematically investigated by the X-ray photoelectron spectroscopy analysis, NH₃ temperature programmed desorption, H₂ temperature programmed reduction and field emission scanning electron microscopy tests. The key factors that can enhance the SCR are the existence of Ce⁴⁺, large NH₃ adsorption capacity, high and early H₂ consumptions, and suitable microstructures for gas adsorption. Finally, CePO₄ and CeVO₄ catalysts also exhibited relatively strong tolerance of SO₂, and the upward trend about 8% was detected due to the sulfation enhancement by SO₂ for Ce₂(SO₄)₃.