Vanadium pentoxide nanofibers (VNF) and polyaniline nanofibers (PANF) nanofibers are synthesized by electrospinning and rapid chemical polymerization routes, respectively. The electrochemical performances of synthesized nanofibers are evaluated in symmetrical (VNF-VNF, PANF-PANF) and asymmetrical (VNF-PANF) configurations in aqueous KCl (3 M) medium by cyclic voltammetry (CV) and galvanostatic measurements. Both VNF and PANF fibers exhibits pseudocapacitive behavior at the electrode/electrolyte interface. The VNF-PANF asymmetrical device is capable of delivering an energy and power densities of 26.7 Wh kg−1 at 0.22 kW kg−1, respectively which is higher than that of symmetrical configuration of VNF-VNF (5.2 Wh kg−1 at 0.22 kW kg−1). In addition, VNF-PANF asymmetrical supercapacitor retained 73% of specific capacitance after 2000 cycles. These results clearly shows that high energy density supercapacitor can be constructed utilizing transitional metal oxides with conducting polymers as electro-active materials in an asymmetrical configuration in aqueous medium.