The development of wide-temperature catalyst with glorious activity and the resistance of SO2 for NH3-SCR reaction are of great importance. However, the preparation of wide-temperature catalyst with outstanding NH3-SCR performance and the resistance of SO2 is still challenging. In this work, Mn and Ce modified IM-5 molecular sieve catalyst (MC-5) was synthesized by incipient wetness impregnation method and the relationship of structure-activity was studied. MC-5 exhibited superior NOx conversion and it was more than 87% in the temperature range of 150-500 °C and ca. 100% at 225 °C due to the high concentration of Mn4+ and chemisorbed oxygen, the excellent redox ability and the synergistic effect of Mn and Ce. Meanwhile, the redox cycle of Mn4++Ce3+↔Mn3++Ce4+ promoted the electron transfer. 27Al NMR spectra and NH3-TPD confirmed Mn ion was mainly located on the bridge hydroxyl group (Brønsted acid sites). The localization energies ΔE of (Al, Mn) for IM-5 was determined by theoretical calculation and the reaction mechanism of M-5 catalyst on Brønsted acid sites was proposed. The reaction mechanism of M-5 catalyst on Brønsted acid sites followed L-H mechanism. And interestingly enough, the NH3-SCR activity of MC-5 significantly increased in the presence of SO2 at 200 °C. One of the reasons was that Ce binded more easily to SO42- and thus protected the active site Mn from sulfation. The other reason was the generation of more acid sites.