Due to the poor water oxidation kinetics and delayed carrier migration efficiency of the BiVO 4 photocatalyst, its photocatalytic H 2 O 2 generation and further utilization as the photoanode in self-powered H 2 O 2 fuel cells are limited. In this study, BiVO 4 (BVO) electrodeposited on indium−tin oxide (ITO) in combination with the photoreduction of silver nanoparticles (Ag NPs) has been successfully prepared and then employed as the photoanode to construct an efficient photocatalytic H 2 O 2 fuel cell system. The photocatalytic H 2 O 2 production and cell performance of Ag NP-decorated BVO (ABVO) photoanode are explored in the electrolyte of 0.2 mol L −1 phosphate buffer solution under AM 1.5G (1 sun, 100 mW cm −2 ) solar irradiation at atmosphere. After the optimization of photoreduction time for Ag NP decoration, the maximum power density of the 20 ABVO-based cell is up to 0.122 mW cm −2 , which has around 2.0 times enhancement compared with pure BVO (0.060 mW cm −2 ). The localized surface plasmon resonance effect of Ag NPs plays an important role in increasing near-field enhancement-induced excitation efficiency, as well as the heterojunction formation between Ag NPs and BVO to effectively promote the generation and migration of photogenerated holes for improving H 2 O 2 production through the water oxidation reaction. This work provides a feasible approach to construct the efficient photoanode for H 2 O 2 production and further develop high-performance photocatalytic H 2 O 2 fuel cells to realize solar energy conversion and utilization.