Vanadium pentoxide (V2O5) nanofibers (VNF) were synthesized through a simple electrospinning method, and their application as supercapacitor electrodes demonstrated. The effect of annealing temperature on the microstructure and morphology of VNF was investigated systematically through scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) surface area measurements. Electrochemical properties of the synthesized products as electrodes in a supercapacitor device were studied using cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy in aqueous electrolyte of different pH and also in an organic electrolyte. The highest specific capacitance was achieved for VNF annealed at 400 degrees C, which yielded 190 F g(-1) in aqueous electrolyte (2 M KCl) and 250 F g(-1) in organic electrolyte (1 M LiClO4 in PC) with promising energy density of 5 Wh kg(-1) and 78 Wh kg(-1) respectively.