A series of poly(3,4-ethylenedioxythiophene) (PEDOT)/V2O5 nanocomposites are prepared via the redox intercalative polymerization reaction of 3,4-ethylenedioxythiophene (EDOT) monomer and crystalline V2O5 within 10min by using rapid 2.45GHz microwave irradiation with full power (800W). The unique properties of the resultant nanocomposites are investigated by various characterization techniques using powder XRD, TGA/DTA and four-point probe conductivity analysis supports the intercalation of polymer nanosheet between V2O5 layers leading to enhanced bi-dimensionality. X-ray photoelectron spectroscopy analysis clearly shows the presence of mixed valent V4+/V5+ in the V2O5 framework after the redox intercalative polymerization which also confirms charge transfer from the polymer to the V2O5 framework. The application potential of these composites as cathode materials in rechargeable lithium batteries is also demonstrated by the electrochemical intercalation of lithium into the PEDOT/V2O5 nanocomposites, where an enhancement in the discharge capacity (370mAh/g) is observed compared to that of crystalline V2O5.