Organic electrode materials suffer from low electronic conductivity and poor structure stability. Herein, a metal–organic polymer, Ni‐coordinated tetramino‐benzoquinone (Ni‐TABQ), is synthesized via d–π hybridization. The polymer chains are stitched by hydrogen bonds to feature as a robust two‐dimensional (2D) layered structure. It offers both electron conduction and Na+ diffusion pathways along the directions of the polymer chains and the hydrogen bonds. With both the conjugated benzoid carbonyls and imines as the redox centers for the insertion and extraction of Na+, the Ni‐TABQ delivers high capacities of about 469.5 mAh g−1 at 100 mA g−1 and 345.4 mAh g−1 at 8 A g−1. The large capacities are sustained for 100 cycles with almost 100 % coulombic efficiencies. The exceptional electrochemical performance is attributed to the unique 2D electron conduction and Na+ diffusion pathways enabled by the robust Ni–N and hydrogen bonds. A metal–organic polymer is synthesized via d–π hybridization. It features a two‐dimensional layered structure by nickel–nitrogen and hydrogen bonds and promises good electrochemical performance with abundant redox centers of conjugated benzoid carbonyls and imines.