A new generation of energy storage material based on electroactive oligomeric supramolecule has been proposed as a proton battery or an aqueous electrochemical capacitor material. A crystalline supramolecular oligomer of 1,5-diaminoanthraquinone (DAAQ) was successfully prepared as a thin film by electrochemical oxidation from an acidic non-aqueous medium. The resulting DAAQ oligomer film exhibited a specific capacity as high as 45–50Ahkg−1 in 4M H2SO4 aq. The redox reaction involves those of the quinone and the π-conjugated system in the DAAQ oligomer which occur separately and/or cross over with exchanging three protons per monomer unit.