The synthesis and characterization of high conductive polyaniline/clay hybrid nanocomposite with extended chain conformation are presented in this paper. The conductive emeraldine salt form of polyaniline is inserted into the layers of montmorillonite clay to produce the hybrid with high conductivity. The properties of the hybrid are characterized by X-ray diffraction, FT-IR, conductivity measurement, qualitative and quantitative analysis of electron absorption spectra; the results show that what we obtain is really a nanocomposite and over 90% of the polyaniline chain is inserted between the layers. Owing to the confined environment in the nanometer size layers of the nanocomposite polyaniline is a single chain with extended-chain conformation.