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A new class of oxyhalide photocatalysts xBiOBr–(1−x)BiOI prepared by a soft chemical method were characterized by X-ray diffraction and UV–Vis diffuse reflectance spectra. They are all visible-light-responsive materials with the bandgaps ranging from 1.92 to 2.91eV. Methyl orange (MO) photocatalytic degradation experiments showed that BiOBr possessed a higher photocatalytic activity than P25 (TiO 2 ) under UV illumination and iodine-modified BiOBr exhibited high photocatlytic activities under visible-light irradiation. The high photocatalytic activity is in close relation with the deep valance band edge position and the internal electric fields between [Bi 2 O 2 ] slabs and halogen anionic slabs.