The　efficient　polymeric　semiconducting　photocatalyst　for　solar-driven　sluggish　kinetics　with　multielectron　transfer　oxygen　evolution　has　spurred　scientific　interest.　However,　existing　photocatalysts　limited　by　π-conjugations,　visible-light　harvest,　and　charge　transfer　often　compromise　the　O2　production　rate.　Herein,　we　introduced　an　alternative　strategy　involving　a　boranil　functionalized-based　fully　π-conjugated　ordered　donor　and　acceptor　(D–A)　covalent　organic　frameworks　(Ni-TAPP-COF-BF2)　photocatalyst.　The　co-catalyst-free　Ni-TAPP-COF-BF2　exhibits　an　excellent　~11-fold　photocatalytic　water　oxidation　rate,　reaching　1404　μmol　g−1　h−1　under　visible　light　irradiation　compared　to　pristine　Ni-TAPP-COF　(123　μmol　g−1　h−1)　alone　and　surpasses　to　reported　organic　frameworks　counterpart.　Both　experimental　and　theoretical　results　demonstrate　that　the　push/pull　mechanism　(metalloporphyrin/BF2)　is　responsible　for　the　appropriate　light-harvesting　properties　and　extending　π-conjugation　through　chelating　BF2　moieties.　This　strategy　benefits　in　narrowing　band　structure,　improving　photo-induced　charge　separation,　and　prolonged　charge　recombination.　Further,　the　lower　spin　magnetic　moment　of　M-TAPP-COF-BF2　and　the　closer　d-band　center　of　metal　sites　toward　the　Fermi　level　lead　to　a　lower　energy　barrier　for　*O　intermediate.　Reveal　the　potential　of　the　functionalization　strategy　and　opens　up　an　alternative　approach　for　engineering　future　photocatalysts　in　energy　conversion　applications.　©　2024　Wiley-VCH　GmbH.