In this study, Mn-Ce-Ox/γ-Al2O3 supported catalysts were adopted to promote the removal efficiency of aniline in simulated wastewater with ozone. Mn-Ce-Ox/γ-Al2O3 catalysts were prepared by the impregnation-calcination method. Its phase structure, specific surface area, loading amount and distribution of active units were analyzed by XRD, BET, ICP-AES and TEM/SEM respectively. The characterization results demonstrated that the catalysts had a good dispersion of Mn-Ce-Ox active sites and an abundant porous structure from the γ-Al2O3 support. The catalytic ozonation results showed that with Mn3-Ce1-Ox/γ-Al2O3(1.0), the aniline removal efficiency was highly improved, 15.0% higher than that of ozonation without a catalyst. Furthermore, from the variation in loading amounts of Mn and Ce, it can be seen that the molar ratio of Mn and Ce within the Mn-Ce-Ox plays a key role in accelerating the ozonation of aniline in simulated wastewater with ozone, while Mn:Ce = 1.9:1 showed the best performance. More importantly, the catalysts showed high recycling performance and could be reused at least 12 times without obvious loss of activity.