Two kinds of BiOBr nanosheets-assembled microspheres were successfully prepared via a facile, rapid and reliable microwave-assisted solvothermal route, employing Bi(NO3)(3)center dot 5H(2)O and cetyltrimethylammonium bromide (CTAB) as starting reagents in the absence or presence of oleic acid. The phase and morphology of the products were characterized by powder X-ray diffraction (XRD), energy dispersive spectrometry (EDS), selected area electron diffraction (SAED), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM). Experiments indicated that the formation of these building blocks of microspheres could be ascribed to the self-assembly of nanoparticles according to mesocrystal growth mode. Interestingly, both samples exhibited not only strong adsorption abilities, but also excellent photocatalytic activities for methyl orange (MO), rhodamine B (RhB) and phenol. The resulting BiOBr hierarchical microspheres are very promising adsorbents and photocatalysts for the treatment of organic pollutants. (C) 2010 Elsevier Inc. All rights reserved.