In this work, hierarchical nanostructures Fe(III)-modified BiOBr were successfully prepared via a facile one-step route at room temperature. Compared with pure BiOBr, Fe(III)-modified BiOBr samples possess enhanced photocatalytic abilities for benzyl alcohol oxidation and organic dye degradation in the presence of H2O2 upon light illumination. The improved photocatalytic oxidation and degradation ability of Fe(III)-modified BiOBr is ascribed to the enhanced photogenerated carriers separation efficiency and promoted production of OH due to the generation of Fe2+ ions via interfacial charge transfer from Fe3+ ions. This work provides a facial approach to improve photocatalytic efficiency for organic synthesis and environmental remediation.