Polyimide　(PI)　has　been　recognized　as　a　potential　organic　cathode　for　Li-ion　batteries　(LIBs)　due　to　its　programmable　structural　design,　high　theoretical　capacity,　and　resource　availability.　However,　the　poor　intrinsic　electrical　conductivity　of　PI　means　that　PI-based　cathodes　of　LIBs　have　inefficient　energy　storage　performance,　especially　at　high　current　densities.　In　this　work,　the　molecular　structure　of　PI　is　optimized　to　obtain　a　layer-stacked　crystalline　PI　with　significantly　enhanced　dipoles,　denoted　NT-B　for　the　first　time.　The　dipoles　in　this　PI　are　induced　by　the　electronegative　carbonyl　groups　from　the　monomer　biuret　and　further　enhanced　via　a　π-π　layer　stacking　effect.　This　work　is　the　first　to　verify　that　the　co-directional　dipole　enhancement　effect　of　biuret　is　surprisingly　different　from　that　of　monomer　urea.　A　series　of　ex-situ/in-situ　and　theoretical　DFT　simulations　are　carried　out　to　understand　the　functional　mechanism　of　such　effects.　The　multiple　enhancement　effects　of　the　dipoles　synergistically　promoting　the　generation　of　a　strong　built-in　electric　field　(BIEF)　within　NT-B　are　proposed　based　on　the　results　obtained.　It　is　confirmed　that　this　BIEF　plays　a　significant　role　in　accelerating　electron　transport,　which　enhances　the　electrochemical　activity　of　LIB　cathodes.　This　work　provides　a　new　idea　for　the　structural　design　of　high-performance　PI　cathodes　for　LIBs.　©　2024　Elsevier　B.V.