Hybrid compounds formed by aniline as the organic phase and Fe rich montmorillonite have been prepared by conventional solution process and a novel solid state intercalation method reported recently in the literature. The structure of hybrids depends closely on the process of preparation. In fact, contrary to conventional solution intercalation method, solid solid reaction favours the intercalation of anilinium cations together with aniline chloride neutral species. In addition, aniline species intercalated by this method are able to polymerize in the interlayer space of clay after 9 weeks without the use of any initiator of polymerization, however, the structure of hybrid compounds prepared by conventional solution method did not change. The aging time is accompanied by the reduction of structural Fe(III) to Fe(II) for hybrids prepared by solid reaction. The structure and electrical properties of the obtained polyaniline/clay nanocomposites have been studied. It was shown that ac conduction shows a regime of constant dc conductivity at low frequencies and a crossover to a frequency-dependent regime of the type A ωS at high frequencies.