In this study, Mn-Ce/Al2O3/TiO2 catalyst prepared by impregnation method was used for synergistic O3 oxidation NO. The catalyst prepared by impregnating Al2O3/TiO2 at a Mn:Ce molar ratio of 4:1 showed the best catalytic activity. The catalyst performance showed that when the molar ratio of Mn:Ce was 4:1 and the volume ratio of O3:NO was 1:4, the removal rate of NO could reach 63%, which could increase the removal rate by 40% compared with that of NO oxidized by O3 alone. BET, XRD, and TEM characterization results showed that when the molar ratio of Mn:Ce was 4:1, the catalyst specific surface area, and pore capacity were the largest. A large amount of MnOx and CeOx were distributed on the catalyst surface. The XPS analysis showed that the oxidation-reduction and oxygen vacancy of Mn (IV)/Mn (III)/Mn (II) and Ce (IV)/Ce (III), had a synergistic effect on the decomposition of O3 into reactive oxygen species(O*), thus improving the catalytic capacity of Mn-Ce/Al2O3/TiO2 catalyst for O3. The O2-TPD analysis showed that the oxygen vacancies and oxygen species in the catalyst could be used as the active point of decomposition of O3 into O*. The experimental results show that the prepared catalyst can significantly improve the efficiency of ozone oxidation of NO and reduce the amount of ozone. The catalyst can be applied to ozone oxidation denitrification technology.