Simultaneous optimization of the number and intensity of oxygen (O2) adsorption on gold (Au) cocatalyst is highly required to greatly improve their interfacial hydrogen peroxide (H2O2)-production activity. However, it is a great challenge to realize the above effective modulation of Au by traditional photodeposition route. In this study, a platinum (Pt)-induced selective photodeposition method was designed to simultaneously regulate the particle size and electronic structure of Au cocatalyst for boosting the photocatalytic H2O2-production activity of bismuth vanadate (BiVO4) via the selective deposition of Pt@Au core–shell cocatalyst. The photocatalytic results indicate that the as-prepared BiVO4/Pt0.1@Au photocatalyst achieves a considerable H2O2-production activity with a rate of 2752.13 μmol L−1 (AQE = 13.76 %), which is obviously higher than that of BiVO4/Pt (137.63 μmol L−1) and BiVO4/Au (475.33 μmol L−1). It was found that the introduction of Pt successfully induced the formation of Au nanoparticles for enhancing the number of O2 adsorption. Meanwhile, the spontaneous transfer of free electrons of Au to Pt induces the generation of electron-deficient Auδ+ sites, which spontaneously enhances the O2-adsorption intensity for facilitating the 2-electron oxygen reduction reaction (ORR), resulting in efficient H2O2 production. The present strategy may be useful for more comprehensively regulating the intensity and number of O2 adsorption on cocatalysts to facilitate artificial photosynthesis.