In this paper, to further promote the photocatalytic performance of BiPO4, BiOBr was employed to couple with BiPO4. Rod-like BiOBr/BiPO4 composites with improved photocatalytic performance were facilely constructed by one-pot hydrothermal method. The composites were characterized by Brunauer -Emmett-Teller (BET) method, X-ray diffraction patterns (XRD), UVeVis diffuse reflectance spectra (DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), surface photovoltage spectroscopy (SPS) and electron spin-resonance (ESR) spectroscopy. The photocatalytic performance of the samples towards degradation of rhodamine B (RhB) and phenol aqueous solution was evaluated under the simulated sunlight irradiation. The SPS results reveal that the separation of photogenerated electron-hole pairs has been promoted due to the formation of heterojuctions. The ESR measurements demonstrate that OH center dot and h(+) are involved in the photocatalytic reaction. The photocatalytic evaluation display that the sample with molar ratio of Br-/PO43- = 0.4% holds the highest activity. The results further substantially exhibit that coupling BiPO4 with BiOBr can remarkably boost the photocatalytic performance of BiPO4, benefiting from significantly enhanced separation of photoinduced charge pairs. Based on all the observations, a Z-scheme separation and transfer scheme of the photoinduced charge pairs of BiOBr/BiPO4 was proposed. (C) 2017 Elsevier B.V. All rights reserved.