The low electronic conductivity of organic electrode materials leads to sluggish reaction kinetics and inferior electrochemical performance of lithium-ion batteries. Herein, the conducting three-dimensional metal–organic framework (3D-MOF) (NBu 4 ) 2 Fe 2 (DHBQ) 3 was synthesized through a facile aqueous addition reaction. The intramolecular charge delocalization through the robust π–d conjugation between DHBQ ligands and Fe 3+ centers is favorable for long-range electron migration, resulting in high electronic conductivity of the 3D hollow (NBu 4 ) 2 Fe 2 (DHBQ) 3 . When applied as the cathode material, (NBu 4 ) 2 Fe 2 (DHBQ) 3 delivers a reversible capacity of 137.2 mA h g –1 at 10 mA g –1 and 95.2 mA h g –1 at 1000 mA g –1 . The capacity retention reached up to 91.4% after 350 cycles at 500 mA g –1 with about 100% Coulombic efficiency. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy tests reveal that the conjugated carbonyls of DHBQ organic linkers contribute the redox centers and undergo a 5e – reaction mechanism during charge and discharge processes. These excellent electrochemical performances could be attributed to the fast electron/ion migration kinetics because of high electronic conductivity and the hollow structure of (NBu 4 ) 2 Fe 2 (DHBQ) 3 . All the positive results could facilitate the implementation of conductive MOFs for energy conversion and storage acceleration.