Hierarchical flower-like BiOBr microspheres assembled with nanosheets were synthesized via solvothermal method with both two-component solvent (ethylene glycol and isopropanol) and CTAB surfactant. The growth of BiOBr crystal was significantly influenced by the concentration of ethylene glycol and isopropanol in two-component solvent, the amount of CTAB surfactant and the solvothermal time. According to the photodegradation of rhodamine B (RhB) under visible-light irradiations, the high photocatalytic activity of hierarchical flower-like BiOBr microspheres could be ascribed to the enhanced visible-light absorbance via the light multi-reflections, the efficient separation of photo-generated electrons and holes, the high crystallization and the large surface area. The main active species during the photocatalytic reaction was determined as O-center dot(2)- radical by additionally dissolving the trapping agent in the solution. Meanwhile, BiOBr microspheres also exhibited the excellent durability owing to the stable crystal phase and microsphere morphology. (C) 2011 Elsevier B.V. All rights reserved.