Mn-Ce/CeAPSO-34 was prepared, in which manganese and cerium were supported on the surface through using the Ethanol dispersion method, while cerium was incorporated in the SAPO-34 framework by a one-step hydrothermal method. Based on our previous study, a strong synergistic effect of cerium presented in the framework and the surface was existing in Mn-Ce/CeAPSO-34 catalyst, which showed outstanding SO_2 tolerance and H_2O resistance in the low-temperature NH_3-SCR. In situ FT-IR and DFT calculations were used to investigate the synergistic effects. Based on the characterization results of in situ FT-IR study, it was found that more amount of nitrate species and NH_3 species adsorbed on the surface of Mn-Ce/CeAPSO-34, while less the amount of sulfate species deposited during reaction process, which in the presence of SO_2. Meanwhile, DFT calculations revealed that Ce site supported on the surface, which neighbored by Ce site in the framework more were capable of reacting with NO and NH_3.