AbstractDirect photoelectrochemical 2‐electron water oxidation to renewable H2O2production on an anode increases the value of solar water splitting. BiVO4has a theoretical thermodynamic activity trend toward highly selective water oxidation H2O2formation, but the challenges of competing 4‐electron O2evolution and H2O2decomposition reaction need to overcome. The influence of surface microenvironment has never been considered as a possible activity loss factor in the BiVO4‐based system. Herein, it is theoretically and experimentally demonstrated that the situ confined O2, where coating BiVO4with hydrophobic polymers, can regulate the thermodynamic activity aiming for water oxidation H2O2. Also, the hydrophobicity is responsible for the H2O2production and decomposition process kinetically. Therefore, after the addition of hydrophobic polytetrafluoroethylene on BiVO4surface, it achieves an average Faradaic efficiency (FE) of 81.6% in a wide applied bias region (0.6–2.1 V vs RHE) with the best FE of 85%, which is 4‐time higher than BiVO4photoanode. The accumulated H2O2concentration can reach 150 µmat 1.23 V versus RHE under AM 1.5 illumination in 2 h. This concept of modifying the catalyst surface microenvironment via stable polymers provides a new approach to tune the multiple‐electrons competitive reactions in aqueous solution.