LAUSR

The sluggish ion‐transport in electrodes and low utilization of active materials are critical limitations of organic cathodes, which lead to the slow reaction dynamics and low specific capacity. In this study, the hierarchical tube is constructed by iron‐hexaazatrinaphthalene tricarboxylic acid coordination polymer (Fe‐HATNTA), using HATNTA as the self‐engaged template to coordinate with Fe2+ ions. This Fe‐HATNTA tube with hierarchical porous structure ensures the sufficient contact between electrolyte and active materials, shortens the diffusion distance, and provides more favorable transport pathways for ions. When employed as the cathode for rechargeable Li‐ion batteries, Fe‐HATNTA delivers a high specific capacity (244 mAh g−1 at 50 mA g−1, 91% of theoretical capacity), excellent rate capability (128 mAh g−1 at 9 A g−1), and a long‐term cycle life (73.9% retention over 3000 cycles at 5 A g−1). Moreover, the Li+ ions storage and conduction mechanisms are further disclosed by the ex situ and in situ characterizations, kinetic analyses, and theoretical calculations. This work is expected to boost further enthusiasm for developing the hierarchical structured metal‐organic coordination polymers with superb ionic storage and transport as high‐performance organic cathodes.