BiVO₄ film was synthesized via template method, the ferroelectric material BiFeO₃ was prepared by Sol-Gel method to modify BiVO₄. By means of dual-ferroelectric semiconductor composition, the photochemical properties of BiVO₄ was greatly improved. The electrochemical test results show that the superior photoelectrochemical properties of BiVO₄ film are achieved after spin-coating with BiFeO₃ for 5 times. It owns an optimal photocurrent density of 0.72 mA·cm^-2, which is 67.4% higher than that of pure BiVO₄. The energy band bending regulation via electric field polarization could further boost the photoelectrochemical property of BiVO₄/nBiFeO₃ ferroelectric composite. The highest photocurrent density of the composite after polarization at 20 V reaches 0.91 mA·cm^-2, which is more than twice of pure BiVO₄ film. The combination of BiFeO₃ and BiVO₄ is favorable for forming heterojuncting, generating and separating of photogenic electrons and holes. The electric field polarization regulating band bending accelerates the photogenic charge transfer, which is the main reason for the improved photoelectrochemical properties of ferroelectric composite.