The effect of the electrolyte on the electrochemical utilization of manganese dioxide as active material for electrochemical capacitor was studied by cyclic voltammetry and electrochemical impedance spectroscopy. MnO2-based composite electrodes were characterized in salt-in-water (0.65 M K2SO4, 5 M LiNO3, 0.5 M LiNO3 and 0.5 M Ca(NO3)2) and water-in-salt (5 M LiTFSI (lithium bis-trifluoromethanesulfonimide)) electrolytes. Firstly, no effect of the cation valence on the specific capacitance was observed as similar values were measured in 0.5 M LiNO3 and 0.5 M Ca(NO3)2 aqueous solutions at both low and high scan rate, when a MnO2-based composite electrode was cycled in the pseudocapacitive potential region. Secondly, it was found that in 5 M LiTFSI, a MnO2 electrode is characterized by an extended potential stability window of about 1.4 V and exhibits a high specific capacitance of 239 F g−1 per active material mass at a scan rate of 2 mV s−1. However due to the low ionic conductivity of this solution, the rate capability is limited at high scan rate.