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.