A fabrication of Sb₂S₃ layer as surface modification on pyramidal BiVO₄ film is realized to improve photoelectrochemical (PEC) performance of BiVO₄ photoanode. The Sb₂S₃-modified BiVO₄ film exhibits an increased photocurrent density of 1.1  mA  /  cm² at 1.23 V versus reversible hydrogen electrode and a negative shift of onset potential. Further, the negative shift of flat band potential demonstrates that the role of Sb₂S₃ surface modification is to suppress surface recombination, and thus increased surface separation and hole transfer efficiency are also achieved for the Sb₂S₃-modified BiVO₄ photoanode. Accordingly, the Sb₂S₃ surface modification enhances surface water oxidation kinetics for the BiVO₄ photoanode, resulting in improved PEC performance. These findings inspire further application of Sb₂S₃ into a PEC water splitting system.