A Flexible, conducting polyaniline/V2O5, (I), nanocomposite was prepared by simply mixing water soluble polyaniline, poly-aniline-propane sulfonic acid (PAPSA), with a V2O5 wet gel and drying at room temperature. XRD data showed that the interlayer spacing of (I) is equal to 14 Angstrom. This is consistent with the insertion of monolayer of polyaniline chains in the V2O5 interlayer space. Variable temperature conductivity data of (I) showed a thermal activated conducting behavior which is similar to those of polyaniline and V2O5: The physicochemical and spectroscopic data suggested that the driving force to the formation of PAPSA/V2O5 nanocomposite is molecular self-assembly. PAPSA chain was confined between two oxygen atoms in V2O5 slab to form the nanocomposite (I).