Vanadium pentoxide–reduced graphene oxide (rGO) free-standing electrodes are used as electrodes for supercapacitor applications, eliminating the need for current collectors or additives and reducing resistance (sheet resistance 29.1 Ω □−1). The effective exfoliation of rGO allows improved electrolyte ions interaction, achieving high areal capacitance (511.7 mF cm−2) coupled with high mass loadings. A fabricated asymmetric flexible device based on rGO/V2O5-rGO (VGO) consists of approximately 20 mg of active mass and still delivers a low equivalent series resistance (ESR) of 3.36 Ω with excellent cycling stability. A prototype unit of the assembled device with organic electrolyte is shown to light up eight commercial light-emitting diode bulbs.