Hexagonal ZnIn2S4 porous microspheres were synthesized via a cetylpyridinium bromide (CPBr)-assisted hydrothermal method. The structure, morphology and optical property of these prepared products were characterized by wide angle X-ray diffraction (WAXRD), small angle X-ray diffraction (SAXRD), UV-Vis diffusive reflectance spectroscopy (DRS), field emission scanning electron microscopy (FESEM), energy dispersive X-ray analyzer (EDX) and nitrogen sorption analysis. The effects of CPBr and pH on the crystal structure, morphology and photocatalytic activity of ZnIn2S4 products were studied. The results demonstrated that the flowerlike ZnIn2S4 microspheres, which were composed of numerous nanosheets, performed higher visible-light photocatalytic activity than bulk ZnIn2S4 for hydrogen evolution. The CPBr addition influenced the crystal structure including the position and intensity of some peaks. Furthermore, the pH played a crucial role in the formation of ZnIn2S4 porous microspheres. The assynthesized porous ZnIn2S4 microspheres possessed the specific surface area of 165.4 m(2) g(-1), and the slit-like porous configuration, which was beneficial to photocatalytic reaction. (C) 2011 Elsevier Ltd. All rights reserved.