Bi/BiVO4 photoelectrode was prepared on FTO glass by the combination of electrochemical deposition, heating treatment and photo-assisted reduction method at room temperature. All of the samples were characterized by X-ray diffraction spectrum (XRD), scanning electron microscope (SEM) and UV-vis diffuse reflectance spectrum (DRS), respectively. The results indicated that metallic Bi particles were well deposited on porous BiVO4 film during the deposition process of photo-assisted reduction, resulting in a greatly broadened visible light absorption edge than that of BiVO4 alone. The optimized photoelectrochemical (PEC) performance of Bi/BiVO4-60 was further verified by linear scan voltammetry (LSV), current-time (I-t) and incident photon-to-current efficiency (IPCE), respectively. It was conjectured the broadened visible light response range of Bi/BiVO4 PEC system and the increased counteraction against positive charge both were caused by the electron transferred from BiVO4 to Bi, and thus effectively facilitated the separation and transfer of photo-generated carriers and thus promote the PEC water splitting performance. (C) 2017 Elsevier B.V. All rights reserved.