Conjugated　polymers　(CPs)　represent　a　promising　platform　for　photocatalytic　CO2　fixation　owing　to　their　suitable　band　structures　that　meet　the　requirements　of　the　reduction　potential　of　CO2　to　value-added　fuels.　However,　the　photocatalytic　performance　of　CPs　is　rather　restrained　by　the　low　charge　transfer　efficiency.　Herein,　we　rationally　designed　three　CPs　with　a　more　delocalized　electronic　transmission　channel　and　planar　molecular　structure,　which　are　regarded　to　evidently　reduce　the　exciton　binding　energy　(Eb)　and　accelerate　the　internal　charge　transfer　process.　Besides,　the　assembly　of　suitable　electron-output　＇tentacles＇　and　cocatalysts　on　the　surface　of　CPs　could　effectively　facilitate　interfacial　electron　delivery.　Accordingly,　the　optimal　P-2CN　exhibits　an　apparent　quantum　yield　of　4.6　%　at　420　nm　for　photocatalytic　CO2　to　CO.　Further　adjusting　the　amounts　of　cyano　groups　and　cocatalysts,　the　CO　selectivity　could　be　obtained　in　the　range　of　0–80.5　%.　©　2023　Wiley-VCH　GmbH.