Herein, synthesis and characterization of amorphous MnO2 and application in asymmetric aqueous ultracapacitors are reported. Different amorphous manganese oxide (MnO2) materials were synthesized from the reduction of KMnO4 in different media such as ethanol (EtOH) or dimethylformamide (DMF). The electrochemical behavior of amorphous MnO2, labeled MnO2-Et and MnO2-DMF, were studied by using cyclic voltammetry, impedance spectroscopy, and galvanostatic cycling in aqueous electrolyte. XRD, BET, TEM, and SEM characterizations highlighted the amorphous nature and the nanostructuration of these MnO2 materials. BET measurement established that these amorphous MnO2 are mesoporous. In addition, MnO2-Et exhibits a larger specific surface area (168 m2 g−1), a narrower pore diameters distribution with lower diameters compared to MnO2-DMF. These results are in agreement with the electrochemical results. Indeed, MnO2-Et shows a higher specific capacitance and lower impedance in aqueous K2SO4 electrolyte. Furthermore, aqueous asymmetric ultracapacitors were assembled and studied using amorphous MnO2 as positive electrode and reduced graphene oxide (rGO) as negative electrode. These asymmetric systems exhibit an electrochemical stability for more than 20,000 galvanostatic cycles at current density of 1 A g−1 with an operating voltage of 2 V.