Herein, we now report a new rational molecular design strategy and comprehensive study on the performance of next-generation carbonylpyridinium-based redox active materials (Scheme 1). As part of this investigation, we developed the two di-cationic carbonylpyridinium-derivatives 1 and 2 that can stably store up to four electrons per molecule. By increasing the size of aromatic systems, the solubility of the materials is greatly reduced as the result of enhanced π-π stacking potential as well as their dicationic nature. Our studies have revealed that the donor-acceptor (D-A) design in 2 with an electron-donating bithiophene bridge helps to enhance intramolecular charge transfer that improves the electronic conductivity, and the final battery performance. Moreover, to further extend the conjugated system within a polymer backbone, we also developed a new dibrominated building block 3, for the synthesis of a series of conjugated polymers CP1 and CP2. The main chain of these conjugated polymers is expected to reduce the twisting between the thiophene units because of the reduced steric repulsion between bithiophene and the alkynyl linkers, leading to a fairly co-planar extended backbone allowing for an efficient electron-conduction pathway. At the same time, the redox activity will largely be localized on the spatially separated, "pendant" carbonylpyridinium groups. As cathode materials for LIBs, the prepared polymers present remarkably improved cyclability and rate performance, because of their high electrochemical activity and effective suppression of dissolution. Impressively, CP2 delivers not only the highest capacity but also the best cycling stability in this series, reaching up to 540 mAh g -1 after 240 cycles at 0.5 A g -1 , and as such even competing with the best inorganic cathode materials. This work highlights the considerable potential of bio-derived carbonylpyridinium redox-active units for sustainable energy storage applications and provides strategy for how they can be improved in LIBs. Scheme 1. Evolution of carbonylpyridinium based two-electron catholytes from small molecules to conjugated polymers.