Imine-linked　covalent　organic　frameworks　(COFs)　are　popular　candidates　for　photocatalytic　CO2　reduction,　but　high　polarization　of　the　imine　bond　is　less　efficient　for　π-electron　delocalization　between　the　linked　building　units,　leading　to　low　intramolecular　electron　transfer　and　poor　photocatalytic　efficiency.　Herein,　we　present　a　structural　and　electronic　engineering　strategy　through　integrating　the　imine-linked　COF　consisting　of　Zn-porphyrin　and　Co-bipyridyl　units　with　cadmium　sulfide　(CdS)　nanowires　to　form　a　CdS@COF　core-shell　structure.　The　experimental　and　theoretical　results　have　validated　that　CdS　serves　as　the　electron　transfer　channel　through　the　interfacial　electron　effects,　which　induces　photoelectron　transfer　from　Zn-porphyrin　to　CdS　and　subsequent　injection　into　Co-bipyridyl　units　for　CO2　reduction.　The　as-prepared　CdS@COF　generates　4057　μmol　g-1　CO　in　8　h　under　visible-light　irradiation,　which　is　considerably　higher　than　those　of　its　neat　CdS　and　imine-linked　COF　counterparts.　This　work　provides　protocols　to　tackle　intramolecular　charge　transfer　across　polar　linkages　between　photosensitizers　and　active　sites　for　solar-to-chemical　energy　conversion.　©　2022　The　Authors.　Published　by　American　Chemical　Society.