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A heterogeneous composite catalyst Cu2O/{001}TiO2 was successfully prepared by the impregnation–reduction method. With ammonia as the target pollutant, the degradation performance and degradation mechanism analysis of the prepared composite catalyst were investigated, providing technology for the application of photocatalysis technology in ammonia treatment reference. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), specific surface area (BET), fluorescence spectrum (PL) and UV-visible absorption (UV-Vis). The results showed: compared with single {001}TiO2, the addition of Cu2O to form a composite catalyst can reduce the recombination of electron–hole pairs, resulting in increased absorption intensity in the visible light range, decreased band gap width, and finally improved the degradation performance. When the composite ratio is 1 : 10, the specific surface area is the largest, which is 72.51 m2 g−1, and the degradation rate of ammonia is also the highest maintained at 85%. After repeated use for 5 times, the degradation rate of ammonia decreases gradually due to the loss of catalyst and photo-corrosion. In the whole reaction process, surface adsorbed water and associated hydroxyl radical participate in the ammonia degradation reaction, and finally form free hydroxyl radical and NO3−. It provides some theoretical support for ammonia gas treatment, which is of great significance to protect the environment.