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Development of efficient and environmentally benign materials is important to satisfy the increasing demand for energy storage materials. Nanostructured transition-metal oxides are attractive because of their variety in morphology, high conductivity, and high theoretical capacitance. In this work, the nanostructured MnO2 was successfully fabricated using a gel formation process followed by calcination at 400 °C (MNO4) and 700 °C (MNO7) in the presence of air. The suitability of the prepared materials for electrochemical capacitor application was investigated using graphite as an electrode substrate. The chemical, elemental, structural, morphological, and thermal characterizations of the materials were performed with relevant techniques. The structural and morphological analyses revealed to be a body-centered tetragonal crystal lattice with a nano-tablet-like porous surface. The capacitive performances of the MNO4- and MNO7-modified graphite electrodes were examined with cyclic voltammetry and chronopotentiometry in a 0.5 M Na2SO4 aqueous solution. The synthesized MNO7 demonstrated a higher specific capacitance (627.9 F g–1), energy density (31.4 Wh kg–1), and power density (803.5 W kg–1) value as compared to that of MNO4. After 400 cycles, the material MNO7 preserves 100% of capacitance as its initial capacitance. The highly conductive network of nanotablet structure and porous morphologies of MNO7 are most likely responsible for its high capacitive behavior. Such material characteristics deserve a good candidate for electrode material in energy storage applications.