Abstract: The synthesis of vanadium pentoxide nanofibers by electrospinning and the fabrication of electrode materials for rechargeable lithium-ion batteries are described. The nanofiber samples are characterized by the methods of optical and electron microscopy, energy dispersive X-ray elemental analysis, and X-ray diffraction. The cathode material is tested by cyclic voltammetry and charge–discharge cycling. The maximum initial values of the specific capacity are obtained in an open three-electrode cell (163 mA h/g) and in a model of coin-type battery (320 mA h/g).