A facile microwave irradiation method has been successfully developed for the controllable fabrication of BiOX (X = Cl, Br, I) nanostructures in mannitol solution. The morphology and size of BiOX nanostructures could be readily tailored by adjusting the amount of halide, reaction precursor, and mannitol concentration. Mannitol molecule acts as both a capping agent and a cohesive agent in the formation of BiOX nanostructures. A possible two-stage formation mechanism was discussed based on the morphology evolution of BiOI nanostructures obtained in mannitol solution with different concentrations. The as-synthesized BiOX nanostructures exhibit much higher photocatalytic activities than that of commercial TiO2. In particular, flower-like BiOX hierarchical nanostructures display the best photocatalytic performance, which is mainly ascribed to their unique hierarchical structure, high BET surface area, and large band gap. Moreover, BiOX nanostructures also demonstrate superior Cr(VI) removal capacity. The Cr(VI) adsorption behavior was also analyzed by the Langmuir and Freundlich adsorption isotherms. (C) 2013 Elsevier Inc. All rights reserved.