Catalytic wet peroxide oxidation (CWPO) is widely used to remove organic pollutants in industrial wastewater, however, the remained challenges in circulating Fe³⁺/Fe²⁺ ions, inevitably forming iron sludge and massively consuming H₂O₂ limit its applications. Herein, the coupling of CWPO and photocatalytic water oxidation on decahedron BiVO₄ crystals was reported to solve the above challenges. Using spatial photogenerated charge separation between different facets of BiVO₄, efficiently circulating Fe³⁺ to Fe²⁺ was realized with a selectivity of ~100%, which greatly inhibits the formation of iron sludge. Moreover, in-situ formation of H₂O₂ through two-hole-involved photocatalytic water oxidation on BiVO₄ replenishes the H₂O₂ consuming in the CWPO process. The coupling system exhibits a much higher total organic carbon (TOC) removal than the CWPO process in various pollutants, giving an improvement of rate constant to more than 10 times. This work provides a potential coupling route for advanced degradation of organic pollutants in wastewater treatment.