A series CeO2/Al2O3 catalysts was modified with rare earth element (La, Nd, Sm, Gd, and Tm) using extrusion method. The catalytic activities of the obtained catalysts were measured for the selective catalytic reduction (SCR) of NO with NH3 to screen suitable addition of rare earth element. These samples were characterized by X-ray diffraction (XRD), N2 adsorption (N2-BET), NH3 temperature-programmed desorption analyses (NH3-TPD), H2 temperature-programmed reduction (H2-TPR), Raman spectra, pyridine adsorption Fourier-transform infrared (Py-IR) and X-ray photoelectron spectroscopy (XPS), respectively. Results showed that the CeO2/Al2O3 exhibited excellent performance in resisting reactant poisoning caused by vapor and sulfur and the highest catalytic activity (98.35%) at 360 °C when the added Tm/Ce molar ratio is 0.10. The surface acidity of CeO2/Al2O3 catalyst would be enhanced with the addition of rare earth ions. Consequently, rare earth ion was beneficial to catalytic activity at low temperatures and corresponded to similar law. Analysis revealed that the higher number of acid sites and the more Ce3+ were conductive to obtain the excellent NH3-SCR activity.