Photocatalytic　reduction　of　CO2　into　syngas　is　a　promising　way　to　tackle　the　energy　and　environmental　challenges;　however,　it　remains　a　challenge　to　achieve　reaction　decoupling　of　CO2　reduction　and　water　splitting.　Therefore,　efficient　production　of　syngas　with　a　suitable　CO/H2　ratio　for　Fischer–Tropsch　synthesis　can　hardly　be　achieved.　Herein,　bipolaronic　motifs　including　Co(II)-pyridine　N　motifs　and　Co(II)-imine　N　motifs　are　rationally　designed　into　a　crystalline　imine-linked　1,10-phenanthroline-5,6-dione-based　covalent　organic　framework　(bp-Co-COF)　with　a　triazine　core.　These　featured　structures　with　spatially　separated　active　sites　exhibit　efficient　photocatalytic　performance　toward　CO2-to-syngas　conversion　with　a　suitable　CO/H2　ratio　(1:1−1:3).　The　bipolaronic　motifs　enable　a　highly　separated　electron–hole　state,　whereby　the　Co(II)-pyridine　N　motifs　tend　to　be　the　active　sites　for　CO2　activation　and　accelerate　the　hydrogenation　to　form　*COOH　intermediates;　whilst,　the　Co(II)-imine　N　motifs　increase　surface　hydrophilicity　for　H2　evolution.　The　photocatalytic　reductions　of　CO2　and　H2O　thus　decouple　and　proceed　via　a　concerted　way　on　the　bipolaronic　motifs　of　bp-Co-COF.　The　optimal　bp-Co-COF　photocatalyst　achieves　a　high　syngas　evolution　rate　of　15.8 mmol　g−1　h−1　with　CO/H2　ratio　of　1:2,　outperforming　previously　reported　COF-based　photocatalysts.　©　2024　Wiley-VCH　GmbH.