Herein, we propose a simple and effective fluoride (F-) ions post-treatment method to improve the solar water splitting performance of BVO. The surface modification of BVO with functional F- ions not only facilitates the transfer and separation efficiency of carriers at the electrode/electrolyte interface but also promotes the adsorption and activation of water, resulting in a photocurrent of 3.2 mA/cm2 at a bias voltage of 1.2 VRHE. Furthermore, the transfer and separation of carriers in the bulk and on the surface are further regulated by the oxygen vacancies induced by F- ions, thereby enhancing the PEC water splitting performance of BVO. Notably, the experimental findings demonstrate that the inclusion of F- ions in the KBi electrolyte enhances the photo-charging process of BVO. Specifically, at a bias voltage of 0.6 VRHE, the BVO-0.12F sample exhibits a stable photocurrent of 1.2 mA/cm2, which is twice as high as that of the initial BVO sample. Remarkably, our study unveils that the addition of F- ions into the KBi electrolyte solution plays a pivotal role in facilitating the separation of charge carriers and promoting interfacial charge transport. Consequently, this further leads to a substantial enhancement in the solar water splitting performance for BVO-0.12F photoanode.