BiFeO(3)and Bi/BiFeO(3)cubic microcrystals were synthesized in this work. The phase, microstructure, optical and photo electrochemical properties, as well as the photocatalytic activities in photocatalytic hydrogen generation were investigated. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results demonstrate the successful synthesis of BiFeO(3)and Bi/BiFeO3. The scanning electron microscope (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray (EDX) results give the evidence of cubic morphology and the deposition of metal Bi on the surface of BiFeO3. The absorption spectra show that Bi/BiFeO(3)has longer absorption edge and stronger absorption capability to visible light. The photocurrent curves, emission spectra, and electrochemical impedance spectroscopy (EIS) spectra demonstrate that Bi/BiFeO(3)has higher efficiency of electron-hole separation and charge transfer, as well as longer lifetime of the charge carriers. These benefit to the enhancement of activity in photocatalytic hydrogen generation.