For　the　efficient　degradation　of　organic　pollutants　with　the　goal　of　reducing　the　water　environment　pollution,　we　employed　an　alkaline　hydrothermal　treatment　on　primeval　g-C3N4　to　synthesize　a　hydroxyl-grafted　g-C3N4　(CN-0.5)　material,　from　which　we　engineered　a　novel　Fenton-like　catalyst,　known　as　Cu–CN-0.5.　The　introduction　of　numerous　hydroxyl　functional　groups　allowed　the　CN-0.5　substrate　to　stably　fix　active　copper　oxide　particles　through　surface　complexation,　resulting　in　a　low　Cu　leaching　rate　during　a　Cu–CN-0.5　Fenton-like　process.　A　sequence　of　characterization　techniques　and　theoretical　calculations　uncovered　that　interfacial　complexation　induced　charge　redistribution　on　the　Cu–CN-0.5　surface.　Specifically,　some　of　the　π　electrons　in　the　tris-s-triazine　units　were　transferred　to　the　copper　oxide　particles　along　the　newly　formed　chemical　bonds　(C(π)-O-Cu),　forming　a　π-deficient　area　on　the　tris-s-triazine　plane　near　the　complexation　site.　In　a　typical　Cu–CN-0.5　Fenton-like　process,　a　stable　π-π　interaction　was　established　due　to　the　favorable　positive-negative　match　of　electrostatic　potential　between　the　aromatic　pollutants　and　π-deficient　areas,　leading　to　a　significant　improvement　in　Cu–CN-0.5＇s　adsorption　capacity　for　aromatic　pollutants.　Furthermore,　pollutants　also　delivered　electrons　to　the　Cu–CN-0.5　Fenton-like　system　via　a　“through-space”　approach,　which　suppressed　the　futile　oxidation　of　H2O2　in　reducing　the　high-valent　Cu2+　and　significantly　improved　the　generation　efficiency　of　•OH　with　high　oxidative　capacity.　As　expected,　Cu–CN-0.5　not　only　exhibited　an　efficient　Fenton　degradation　for　several　typical　aromatic　organic　pollutants,　but　also　demonstrated　both　a　low　metal　leaching　rate　(0.12　mg/L)　and　a　H2O2　utilization　rate　exceeding　80%.　The　distinctive　Fenton　degradation　mechanism　substantiated　the　potential　of　the　as-prepared　material　for　effective　wastewater　treatment　applications.　©　2024