The　precise　regulation　of　photocatalytic　oxygen　reduction　reaction　(ORR)　pathways,　particularly　the　more　energy-efficient　one-step　2e(-)　route,　is　of　fundamental　importance　for　optimizing　H2O2　production　efficiency　in　rationally　designed　covalent　organic　frameworks　(COFs).　Here,　a　strengthened　donor-acceptor　(D-A)　structured　TPCN-COF　[COF　synthesized　from　2,4,6-hydroxy-1,3,5-benzotricarboxaldehyde　and　1,3,5-tris　(4-aminophenyl)　benzene]　photocatalyst　was　developed　through　the　strategic　incorporation　of　pyridine　nitrogen　moieties　into　the　COF　skeleton.　The　strengthened　D-A　structure　facilitates　effective　separation　of　photogenerated　charge　carriers　while　promoting　rapid　electron　transfer　kinetics.　Concurrently,　the　introduced　pyridine　nitrogen　units　increase　the　surface　polarity,　thereby　improving　hydrophilicity　and　enabling　more　efficient　proton　delivery　to　active　sites.　Remarkably,　the　synergistic　combination　of　enhanced　charge　separation　and　optimized　proton　transport　in　TPCN-COF　effectively　shifts　the　ORR　mechanism　from　two-step　1e(-)　pathway　to　one-step　2e(-)　process.　As　a　result,　TPCN-COF　achieves　an　exceptional　H2O2　production　rate　of　1320.9　mu　molg(-1)h(-1)　under　visible　light　irradiation　(lambda　＞=　420　nm)　in　an　air-equilibrated　aqueous　system,　representing　a　nearly　3-fold　enhancement　compared　to　the　unmodified　TPCC-COF　[COF　synthesized　from　2,4,6-hydroxy-1,3,5-benzotricarboxaldehyde　and　5,5　＇,5　＇＇-　(benzene-1,3,5-triyl)　tris　(pyridin-2-ylamino)].　This　work　establishes　an　effective　design　strategy　for　constructing　COFs　photocatalysts　with　strong　D-A　structures,　and　elucidates　the　synergistic　regulatory　mechanism,　by　which　both　electronic　structure　and　surface　properties　govern　ORR　pathway　selectivity　in　COF-based　systems.