Photocatalytic　reduction　of　diluted　CO2　from　anthropogenic　sources　holds　tremendous　potential　for　achieving　carbon　neutrality,　while　the　huge　barrier　to　forming　*COOH　key　intermediate　considerably　limits　catalytic　effectiveness.　Herein,　via　coordination　engineering　of　atomically　scattered　Ni　sites　in　conductive　metal–organic　frameworks　(CMOFs),　we　propose　a　facile　strategy　for　tailoring　the　d-band　center　of　metal　active　sites　towards　high-efficiency　photoreduction　of　diluted　CO2.　Under　visible-light　irradiation　in　pure　CO2,　CMOFs　with　Ni-O4　sites　(Ni-O4　CMOFs)　exhibits　an　outstanding　rate　for　CO　generation　of　13.3　μmol　h−1　with　a　selectivity　of　94.5　%,　which　is　almost　double　that　of　its　isostructural　counterpart　with　traditional　Ni-N4　sites　(Ni-N4　CMOFs),　outperforming　most　reported　systems　under　comparable　conditions.　Interestingly,　in　simulated　flue　gas,　the　CO　selectivity　of　Ni-N4　CMOFs　decreases　significantly　while　that　of　Ni-O4　CMOFs　is　mostly　unchanged,　signifying　the　supremacy　for　Ni-O4　CMOFs　in　leveraging　anthropogenic　diluted　CO2.　In　situ　spectroscopy　and　density　functional　theory　(DFT)　investigations　demonstrate　that　O　coordination　can　move　the　center　of　the　Ni　sites′　d-band　closer　to　the　Fermi　level,　benefiting　the　generation　of　*COOH　key　intermediate　as　well　as　the　desorption　of　*CO　and　hence　leading　to　significantly　boosted　activity　and　selectivity　for　CO2-to-CO　photoreduction.　©　2024　Wiley-VCH　GmbH.