This paper presents the first implementation of electrically conductive metal−organic framework (MOF) Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 (Ni 3 (HITP) 2 ) integrated with nickel bis(diimine) (Ni-BDI) units for efficient solidstate electrochemical carbon dioxide (CO 2 ) capture. The electrochemical cell assembled using Ni 3 (HITP) 2 as working electrodes can reversibly capture and release CO 2 through potential control. A high-capacity utilization of 96% and a Faraday efficiency of 98% have been achieved. The material also exhibits excellent electrochemical stability with its capacity maintained during 50 capture− release cycles and resistance to general interferences, including O 2 , H 2 O, NO 2 , and SO 2 . Capacity utilization of up to 35% is obtained at CO 2 concentrations as low as 1%. The capture of CO 2 at concentrations ranging from 1% to 100% requires exceptionally low energy consumption of only 30.5−72.4 kJ mol −1 . Studies combining spectroscopic experiments and computational approaches reveal that the CO 2 capture and release mechanism involves reversible carbamate formation on the N atom of the Ni-BDI unit in the MOF upon its one-electron redox reaction.