A simple, low cost, and “green” method of hydrothermal synthesis, based on the addition of l-ascorbic acid (l-AA) as a reducing agent, is presented in order to obtain reduced graphene oxide (rGO) and hybrid rGO-MoO₂ aerogels for the fabrication of supercapacitors. The resulting high degree of chemical reduction of graphene oxide (GO), confirmed by X-Ray Photoelectron Spectroscopy (XPS) analysis, is shown to produce a better electrical double layer (EDL) capacitance, as shown by cyclic voltammetric (CV) measurements. Moreover, a good reduction yield of the carbonaceous 3D-scaffold seems to be achievable even when the precursor of molybdenum oxide is added to the pristine slurry in order to get the hybrid rGO-MoO₂ compound. The pseudocapacitance contribution from the resulting embedded MoO₂ microstructures, was then studied by means of CV and electrochemical impedance spectroscopy (EIS). The oxidation state of the molybdenum in the MoO₂ particles embedded in the rGO aerogel was deeply studied by means of XPS analysis and valuable information on the electrochemical behavior, according to the involved redox reactions, was obtained. Finally, the increased stability of the aerogels prepared with l-AA, after charge-discharge cycling, was demonstrated and confirmed by means of Field Emission Scanning Electron Microscopy (FESEM) characterization.