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A series of Bi₄O₅Br₂ photocatalysts were prepared via an innovation method of synthesis with ionic liquids (ILs). The crystal structures were investigated by X-ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR). The Field Emission Scanning Electron Microscope (FE-SEM) images illustrated the unique structure of prepared photocatalysts. The photocatalysts were also characterized by N₂ adsorption-desorption analysis, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (UV-vis/DRS) and photoluminescence spectra (PL). The role of ILs in synthesis of Bi₄O₅Br₂on morphology and photocatalytic properties were investigated. Rhodamine B, 5-fluorouracil and chromium (VI) were used as the model micropollutants to evaluated adsorption capacity, photooxidation and photoreduction ability of prepared Bi₄O₅Br₂ under artificial solar light. This work provided a new thought for enhanced photocatalytic activity of bismuth oxybromide photocatalysts.