Abstract Manganese oxides have attracted great interest in electrochemical energy storage due to high theoretical specific capacitance and abundant valence states. The multiple valence states in the redox reactions are beneficial for enhancing the electrochemical properties. Herein, three manganese microspheres were prepared by a one‐pot hydrothermal method and subsequent calcination at different temperatures using carbon spheres as templates. The trivalent manganese of Mn 2 O 3 exhibited multiple redox transitions of Mn 3+ /Mn 2+ and Mn 4+ /Mn 3+ during the intercalation/deintercalation of electrolyte ions. The possible redox reactions of Mn 2 O 3 were proposed based on the cyclic voltammetry and differential pulse voltammogram results. Mn 2 O 3 microsphere integrated the advantages of multiple redox couples and unique structure, demonstrating a high specific capacitance and long cycling stability. The symmetric Mn 2 O 3 //Mn 2 O 3 device yielded a maximum energy density of 29.3 Wh kg −1 at 250 W kg −1 .