In this paper, the solid-state synthesis of polyaniline/Cu-montmorillonite nanocomposite is reported. Mixture of anilinium chlorure and Cu exchanged montmorillonite was grinded at room temperature while we vary the molar rate of aniline to interlayer Cu(2+). cations (R) from 0.5 to 6. The properties of the hybrid compounds are characterized by X-ray diffraction, thermogravimetric analysis, SEM, FUR and impedance spectroscopy. The results showed that the structure and the conductivity of PANI in hybrid materials depend on R. The ac conduction showed a regime of constant dc conductivity at low frequencies and a crossover to a frequency-dependent regime of the type A omega(s) at high frequencies. (C) 2010 Elsevier Ltd. All rights reserved.