Rationally designed organic redox‐active materials have attracted numerous interests due to their excellent electrochemical performance and reasonable sustainability. However, they often suffer from poor cycling stability, intrinsic low operating potential, and poor rate performance. Herein, a novel Donor–Acceptor (D–A) bipolar polymer with n‐type pyrene‐4,5,9,10‐tetraone unit storing Li cations and p‐type carbazole unit which attracts anions and provides polymerization sites is employed as a cathode for lithium‐ion batteries through in situ electropolymerization. The multiple redox reactions and boosted kinetics by the D–A structure lead to excellent electrochemical performance of a high discharge capacity of 202 mA h g−1 at 200 mA g−1, impressive working potential (2.87 and 4.15 V), an outstanding rate capability of 119 mA h g−1 at 10 A g−1 and a noteworthy energy density up to 554 Wh kg−1. This strategy has significant implications for the molecule design of bipolar organic cathode for high cycling stability and high energy density.