Orienting　electron　transport　to　suppress　charge　recombination　is　attractive　for　efficient　photocatalysis　but　remains　challenging.　Herein,　we　demonstrate　the　synthesis　of　crystalline　linear　conjugated　polyimides　via　the　condensation　of　carboxylic　anhydrides　and　amine　monomers　for　the　photocatalytic　reduction　of　CO2.　Oriented　electron　transport　was　achieved　using　crystalline　polyimides　integrated　with　electronic　push-pull　units.　Directional　intramolecular　electron　transfer　is　driven　by　the　dipole　effects　of　the　adjacent　building　units.　The　sulfone-based　polyimide　exhibited　excellent　photocatalytic　performance　for　CO2　reduction.　Our　work　provides　a　new　example　photoreduction　of　CO2　and　a　strategy　for　developing　efficient　photocatalysts　with　oriented　electron　transport.　©　2023　Dalian　Institute　of　Chemical　Physics,　the　Chinese　Academy　of　Sciences