The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance, abysmal conductivity, and the resultant low practical capacity. To address these issues, a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated. The π-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane, endowing them with good conductivity and reaction reversibility. Furthermore, when the para-positions of phenylene are occupied by hydroxyl groups, as-formed intramolecular hydrogen bonds (N–H…O) between phenolic hydroxyl groups and the –NH groups of imidazole rings further enhance the structural planarity, resulting in higher π-conjugation degree and better conductivity, and thus higher utilization of active sites and electrode capacity, proved by both experimental results and theoretical calculations. The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity (∼308 mA h g−1 at 100 mA g−1) and a long cycling stability (112.9 mA h g−1 after 6000 cycles at 2000 mA g−1). The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.