Polyimide　has　been　regarded　as　a　potential　organic　cathode　for　lithium-ion　batteries　(LIBs)　due　to　its　excellent　solvent　resistance,　thermodynamic　stability　and　flexibly　programmable　polymer　structure.　However,　the　poor　conductivity,　easy　entanglement　and　agglomeration　of　PI　chains　lead　to　slow　ion　diffusion,　poor　electron　transfer,　and　insufficient　reaction,　which　make　it　difficult　to　effectively　exert　its　theoretical　capacity　at　high　current　density.　Herein,　a　layer　stacked　polyimide　cathode　(NT-U)　based　on　π-π　stacking　effect　was　successfully　obtained.　NT-U　possesses　a　large　molecular　dipole　moment　that　induced　by　the　strong　electronegative　groups　in　PI　and　further　enhanced　by　the　π-π　stacking　structure,　which　contributes　to　the　formation　of　a　robust　built-in　electric　field　(BIEF).　The　strong　BIEF　in　this　highly　crystalline　PI　plays　a　critical　role　in　accelerating　the　charge　transport　dynamics　and　improving　electrochemical　performances　of　LIBs,　as　verified　by　in-situ　XRD,　ex-situ　FTIR,　ex-situ　XPS,　and　ex-suit　SEM,　DFT　calculations.　These　findings　provide　new　insights　into　the　construction　of　PIs　cathode　based　on　the　mechanism　of　dipole　and　BIEF　for　fast　and　efficient　energy　storage.　©　2024　Elsevier　B.V.