Photocatalytic technology is considered an ideal approach for clean energy conversion and environmental pollution applications. In this work, a bifunctional BiOBr/ZIF-8/ZnO photocatalyst was proposed for removing phenols in wastewater and generating hydrogen peroxide. Insights from scanning electron microscopy measurements revealed the well-dispersion of ZIF-8/ZnO was on the BiOBr layer, which could effectively prevent agglomeration of ZIF-8 and facilitate the separation of carriers. In addition, the optimal H₂O₂ yield of the BiOBr/ZIF-8/ZnO sample could reach 116 mmol·L⁻¹·g⁻¹ within 2 h, much higher than that of pure BiOBr (with the value of 82 mmol·L⁻¹·g⁻¹). The optimal BiOBr/ZIF-8/ZnO sample could also remove 90% of the phenol or bisphenol A in 2 h, and its kinetic constants were 3.8 times and 2.3 times that of pure BiOBr, respectively. Based on the analysis of the various experimental characterizations, the photocatalytic mechanism of the S-scheme BiOBr/ZIF-8/ZnO composite for the degradation of phenolic pollutants and generation of H₂O₂ was proposed. The formation of the heterojunction and the oxygen vacancy work together to significantly improve its photocatalytic efficiency. In addition, the BiOBr/ZIF-8/ZnO catalyst has a certain impact on the degradation of phenol in actual wastewater, providing a way to effectively remove refractory pollutants and generate H₂O₂ in actual water.