In order to effectively remove nitrobenzene-containing wastewater, nitrobenzene was degraded by heterogeneous Fenton system in this study. CuO/Al₂O₃ catalysts were prepared by different methods and conditions. The characteristics of CuO/Al₂O₃ were analyzed by BET, X-ray diffraction (XRD) and scanning electron microscope (SEM). Among them, the specific surface area, pore volume and pore size of CuO/Al₂O₃ were characterized by BET; the phase and crystallinity of the CuO/Al₂O₃ were determined by XRD; the surface morphology of the CuO/Al₂O₃ was observed by SEM. Nitrobenzene concentration was determined by HPLC. The nitrobenzene-containing wastewater was degraded by a heterogeneous Fenton-Like system catalyzed with prepared CuO/Al₂O₃. The results showed that the optimal preparation method of the catalyst was the deposition precipitation method. The optimal conditions of the catalyst were as follows: the loading content of CuO was 5%, the calcination temperature of CuO was 400ºC, the calcination time of CuO was 3 h, and the calcination temperature of Al₂O₃ carrier was 400ºC. The removal rate of nitrobenzene reached 84.37% under this condition. This study shows that the nitrobenzene could be effectively degraded in a heterogeneous Fenton-like system catalyzed by CuO/Al₂O₃.