Constructing　photocatalytically　active　and　stable　covalent　organic　frameworks　containing　both　oxidative　and　reductive　reaction　centers　remain　a　challenge.　In　this　study,　benzotrithiophene-based　covalent　organic　frameworks　with　spatially　separated　redox　centers　are　rationally　designed　for　the　photocatalytic　production　of　hydrogen　peroxide　from　water　and　oxygen　without　sacrificial　agents.　The　triazine-containing　framework　demonstrates　high　selectivity　for　H2O2　photogeneration,　with　a　yield　rate　of　2111　μM　h−1　(21.11　μmol　h−1　and　1407　μmol　g−1　h−1)　and　a　solar-to-chemical　conversion　efficiency　of　0.296%.　Codirectional　charge　transfer　and　large　energetic　differences　between　linkages　and　linkers　are　verified　in　the　double　donor-acceptor　structures　of　periodic　frameworks.　The　active　sites　are　mainly　concentrated　on　the　electron-acceptor　fragments　near　the　imine　bond,　which　regulate　the　electron　distribution　of　adjacent　carbon　atoms　to　optimally　reduce　the　Gibbs　free　energy　of　O2*　and　OOH*　intermediates　during　the　formation　of　H2O2.　©　2023,　Springer　Nature　Limited.