A group of nanosheet-assembled three-dimensional BiOCl1-xBrx hierarchical microspheres (x=0, 0.3, 0.4, 0.5, 0.7, 0.8 and 1.0) with layered tetragonal crystal phase were prepared by 2-methoxyethanol-assisted solvothermal route and using ionic liquids as both halogen sources and structure-directing agent. By the combination of the results including XRD, XPS and UV-vis/DR spectra, lattice substitution of halogen atoms each other and then formation of BiOCl1-xBrx solid solution was evidenced. Additionally, the BiOCl1-xBrx microspheres exhibited interesting composition-dependent band gaps. The simulated sunlight and visible-light photocatalytic properties including degradation, mineralization and reusability of the BiOCl1-xBrx microspheres were evaluated by selecting p-nitrophenol (PNP) and tetrabromobisphenol-A (TBBPA) as the target pollutant compounds, finding that the balance between the suitable band gap and adequate potential of the valence band in BiOCl1-xBrx crystals dominated their photocatalytic activity. Additionally, the BiOCl1-xBrx microspheres with advantages such as enhanced photon utilization efficiency, larger BET surface area and favorable (110) exposed reactive surface gave the positive influence on their photocatalytic activity. Based on the results of photoelectrochemistry experiment and indirect chemical probe testing, direct O-center dot(2)- and h(VB)(+) photooxidation for the decomposition of PNP or TBBPA was revealed. (C) 2016 Elsevier B.V. All rights reserved.