A nanocomposite comprised of conductive poly(3,4-ethylene dioxythiophene)PEDOT chains interleaved between the layers of crystalline V,05 powder has been synthesized by direct in situ oxidation, The interlayer spacing of V2O5 expands from 4.32 to 13.84 Angstrom and this interlayer separation is consistent with the existence of a monolayer of PEDOT in the V2O5 framework. The nanocomposite is coupled with a large-area Li foil counter electrode and a Li wire reference electrode in I M LiClO4 in a mixture of ethylene and dimethylcorbonate (50150 by volume), the discharge capacity is greater than or equal to300 m Ah g(-1) which is larger than that of pristine V2O5. The significant difference in capacity is explained on the basis of lithium ions insertion/de-insertion between the layers Of V2O5.