In order to improve the lower practical capacity and bad cyclability of crystalline V 2O 5 (c-V 2O 5), the vanadium oxide (V 2O 5) and polypyrrole (PPy) hybrid with hollow-spherical(HS) structure was studied. HS nanocomposite comprised of conductive polypyrrole and vanadium pentoxide (PPy/V 2O 5) was synthesized by polymerization of pyrrole monomer (Py) in the hollow-microspherical V 2O 5 host. This novel hybrid was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and tested as the cathode material for lithium-ion batteries (LIB) by galvanostatic cell cycling and electrochemical impedance spectroscopy (EIS). The hollow-spherical polypyrrole/vanadium oxide (HS-PPy/V 2O 5) composites, in which PPy molecules are intercalated between the layers of V 2O 5, exhibit slight reduced capacity and substantially improve cyclability and electrochemical activity compared with the pure HS-V 2O 5.