In view of the engineering requirements for the co-processing of nitrogen oxides (NO_x) and volatile organic compounds (VOCs) in the flue gas of waste in cement kiln, a series of CuCe-MCM-41 loading catalysts with different Cu/Ce doping ratios were prepared by impregnation method. The performance of catalytic removal of toluene and NO_x in the pre-calcining system of cement kiln and the reasons for its excellent performance were discussed. The results show that the prepared Cu₂Ce₁-MCM-41 catalyst has a toluene conversion rate of more than 90% at 450~600 ℃, and the NO_x conversion rate is close to 60% at 800~1 000 ℃. It shows that the Cu₂Ce₁-MCM-41 catalyst still has a certain denitration activity after catalytic oxidation of toluene. The introduction of Cu²⁺ and Ce³⁺ significantly increases the acidity and the number of active sites on the surface of MCM-41 molecular sieve, and the oxidation reduction cycle promotes the formation of oxygen vacancies. Therefore, the Cu/Ce coading MCM-41 catalyst shows excellent catalytic oxidation of toluene and denitration activity. It is expected to combine the cement process to remove VOCs from flue gas, greatly reduce the NO_x concentration entering the NH₃-SCR flue gas, prolong the service life of catalyst, and reduce NO_x abatement costs.