Synergistic π‐π and π‐d Interactions Between Carbon Nanotubes and Coordination Polymers Crafting Core‐Shell Nanostructured Cathode for High‐Performance Sodium‐Organic Batteries

π‐d conjugated coordination polymers hold promising electrode candidates for advanced sodium‐ion batteries (SIBs) while they commonly encounter challenges such as restricted electron delocalization and utilization of redox‐active sites during electrochemical cycling. Herein, we propose a core‐shell composite (CNT@Ni‐DHBQ) as the cathode for SIBs via in situ polymerization, in which 2,5‐dihydroxy‐1,4‐benzoquinone (DHBQ) serves as the organic ligand, Ni 2+ as the metal center, and carbon nanotubes (CNTs) as conductive scaffolds. The well‐defined core‐shell architecture offers a large specific surface area with numerous exposed sites, enabling fast electron transport and superior rate capability. In addition, robust π‐π stacking between Ni‐DHBQ and conductive CNT framework significantly enhances cycling stability. A reversible carbonyl (C=O) based redox mechanism in CNT@Ni‐DHBQ during cycling is revealed by ex situ X‐ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. This molecular‐ and microstructure‐engineered strategy provides a feasible strategy to boost the energy‐storage performance of organic cathodes in SIBs.