In the present work, we report the difference between the electrochemical behavior of MnO₂ and Mn₂O₃, which are synthesized in the presence and absence of Ni foam, respectively, using simple and facile hydrothermal method. The X-ray diffraction (XRD) patterns of MnO₂ and Mn₂O₃ samples revealed the presence of orthorhombic and cubic phases, with the p n n m and Ia\(\overline{3 }\) space groups, respectively. The FE-SEM showed the 3D leaf-like structure of MnO₂ over the Ni foam and the agglomeration of the powder of the Mn₂O₃ sample. The molecular fingerprint and chemical composition of the MnO₂ and Mn₂O₃ has been confirmed from the Raman spectra and FTIR, respectively. The presence of Mn⁴⁺ and Mn³⁺ oxidation states in MnO₂ and Mn₂O₃, respectively, was verified by XPS results. The electrochemical performances indicate the maximum specific capacitance of MnO₂ and Mn₂O₃, 212 and 338 F/g, at the scan rate of 5 mV/s. Basic Mn₂O₃ is also showing better capacity retention than MnO₂ after 500 cycles in 3 M KOH electrolyte.