Heterojunctions of alternating MnO₂ and NiO thin films were deposited on an Indium Tin Oxide (ITO). The MnO₂ and NiO thin films were synthesized by electrodeposition and sol-gel methods respectively. The structural morphology of the synthesized heterojunctions was investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The microstructural and chemical compositions were examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR), and Raman techniques. The optical properties were investigated by Ultraviolet-Visible (UV) analysis. The electrical conductivity, specific capacitance, and charge carrier density were determined using the Hall effect and Electrochemical impedance spectroscopy (EIS) methods. As a result, it was found that the MnO₂ and NiO thin films crystallize in tetragonal and cubic crystal systems respectively. Increasing the number of NiO/MnO₂ heterojunctions increases the electrical conductivity from 9.7 × 10⁻⁷ to 1.2 × 10⁻³ S.cm⁻¹, the bandgap decreased 3.16 to 2.62 eV, the volume carrier density rises from 5.17 × 10¹¹ to 4.62 × 10¹² cm⁻³. The specimens constituted of two and four alternative staked MnO₂ and NiO layers are characterized by a specific capacitance of 3.6 × 10³ and 5.8 × 10³ F.g ^− 1 and capacitance retention of 14.8 and 12.9% which consider them promising materials for supercapacitor devices.