The oxygen reduction process generating H2O2 in the photoelectrochemical (PEC) system is milder and environmentally friendly compared with the traditional anthraquinone process but still lacks the efficient electron-oxygen-proton coupling interfaces to improve H2O2 production efficiency. Here, we propose an integrated active site strategy, that is, designing a hydrophobic C-B-N interface to refine the dearth of electron, oxygen, and proton balance. Computational calculation results show a lower energy barrier for H2O2 production due to synergistic and coupling effects of boron sites for O2 adsorption, nitrogen sites for H+ binding, and the carbon structure for electron transfer, demonstrating theoretically the feasibility of the strategy. Furthermore, we construct a hydrophobic boron- and nitrogen-doped carbon black gas diffusion cathode (BN-CB-PTFE) with graphite carbon dots decorated on a BiVO4 photoanode (BVO/g-CDs) for H2O2 production. Remarkably, this approach achieves a record H2O2 production rate (9.24 μmol min-1 cm-2) at the PEC cathode. The BN-CB-PTFE cathode exhibits an outstanding Faraday efficiency for H2O2 production of ∼100%. The newly formed h-BN integrative active site can not only adsorb more O2 but also significantly improve the electron and proton transfer. Unexpectedly, coupling BVO/g-CDs with the BN-CB-PTFE gas diffusion cathode also achieves a record H2O2 production rate (6.60 μmol min-1 cm-2) at the PEC photoanode. This study opens new insight into integrative active sites for electron-O2-proton coupling in a PEC H2O2 production system that may be meaningful for environment and energy applications.