The strong Coulombic interactions between Al3+ and traditional inorganic crystalline cathodes present a significant obstacle in developing high-performance rechargeable aluminum batteries (RABs) that hold promise for safe and sustainable stationary energy storage. While accommodating chloroaluminate ions (AlCl4−, AlCl2+ etc.) in redox-active organic compounds offers a promising solution for RABs, the issues of dissolution and low ionic/electronic conductivities plague the development of organic cathodes. Herein, we synthetically connect electron donors with acceptors to create crosslinked, bipolar-conjugated polymer cathodes. These cathodes exhibit overlapped redox potential ranges for both donors and acceptors in highly concentrated AlCl3-based ionic liquid electrolytes. This approach strategically enables on-site doping of the polymer backbones during redox reactions involving both donor and acceptor units, thereby enhancing the electron/ion transfer kinetics within the resultant polymer cathodes. Based on the optimal donor/acceptor combination, the bipolar polymer cathodes can deliver a high specific capacity of 205 mAh g− 1 by leveraging the co-storage of AlCl4− and AlCl2+. The electrodes exhibit excellent rate performance, stable cycle life of 60,000 cycles, and function efficiently at high mass loadings, i.e., 100 mg cm− 2, and at low temperatures, i.e., − 30 oC. Our findings exemplify the exploration of high-performing conjugated polymer cathodes for RABs through rational structural design.