Tubular nanofibers (TNFs) of vanadium pentoxide (V2O5) were synthesized by electrospinning technique using a single spinneret for the first time by controlling the properties of the precursor solution. A partially miscible polymeric solution of vanadium oxytrihydroxide [VO(OH)(3)] was produced by hydrolysis of vanadyl acetylacetonate in Poly(vinylpyrrolidone) (PVP). The phase-separated polymer solution formed the core of the electrospun fibers whereas the VO(OH)(3) formed the shell; the core PVP has been removed by controlled heat treatment. The TNFs had an inner diameter similar to 60 nm and wall thickness similar to+/-100 nm. The capacitive behavior of the V2O5 TNFs was studied using cyclic voltammetry and galvanostatic cycling techniques. The studies showed ideal stable supercapacitive characteristics in the electrospun V2O5 TNFs.