A novel type of semiconductor, FeF₂/BiVO₄ was successfully prepared by electric deposition of precipitating FeF₂ onto the surface of BiVO₄ electrode so as to generate hydrogen during water splitting process. Via a list of trial catalyzed with FeF₂/BiVO₄ containing different contents of FeF₂, the most efficient catalyst was optimised as the one with depositing FeF₂ for 20 circles. Consequently, it able to produce the amount of 635.5 μmol H₂ within 3 h, three times more than BiVO₄ alone. The optimal photoanode of FeF₂/BiVO₄ exhibits a photocurrent density of 2.49 mA cm⁻² at 1.23 V vs. RHE and an IPCE value of 28% at 450 nm, which are 2.26 and 3.73 times as much as pure BiVO₄ photoanode, respectively. It is mainly attributed to the enhanced capacities of light absorption in the visible range and transfer of photo-generated carriers as well as separation between electrons and holes after the combination of BiVO₄ and FeF₂. At the same time, it offers a novel idea toward the project of solar water splitting.