To solve the problems such as the dissolution and the poor conductivity of organic small molecule electrode materials, we construct π‐d conjugated coordination polymer Ni‐DHBQ with multiple redox‐active centers as lithium storage materials. It exhibits an ultra‐high capacity of 9‐electron transfers, while the π‐d conjugation and the laminar structure inside the crystal ensure fast electron transport and lithium ion diffusion, resulting in excellent rate performance (505.6 mAh g−1 at 1 A g−1 after 300 cycles). The interaction of Ni‐DHBQ with the binder CMC synergistically inhibits its dissolution and anchors the Ni atoms, thus exhibiting excellent cycling stability (650.7 mAh g−1 at 0.1 A g−1 after 100 cycles). This work provides insight into the mechanism of lithium storage in π‐d conjugated coordination polymers and the synergistic effect of CMC, which will contribute to the molecular design and commercial application of organic electrode materials. The π‐d conjugated coordination polymer Ni‐DHBQ exhibits an ultra‐high lithium storage capacity of 9‐electron transfer and excellent rate performance due to its multiple redox active centers, π‐d conjugation and laminar structure. Meanwhile, the binder CMC, like an octopus, has an appropriate interaction with both the ligand and Ni2+ of Ni‐DHBQ, thus reducing the solubility of Ni‐DHBQ and enhancing its cycle life.