Polyaniline (PANI)/Ag@AgCl nanocomposites were successfully synthesized by one-step method, which consists of mixing aqueous solutions of silver nitrate with aniline chloride and delaying the evolution of reaction. By this way, aniline chloride represents a monomer for PANI and a source of Cl− anions necessary for the formation of AgCl, and silver nitrate acts simultaneously as oxidant initiator for aniline polymerization and precursor for AgCl@Ag phase. The formation of polyaniline has been identified by the change of color to black green and from RAMAN and FTIR spectroscopy while AgCl@Ag phase has been highlighted from XRD and RAMAN. The application of Debye–Scherrer theory allows us to measure the crystallite sizes of Ag and AgCl which were, respectively, 23 and 52 nm. The AC conductivity showed a regime of constant DC conductivity at low frequencies corresponding to 0.4 S/cm−1 and a crossover to a frequency-dependent regime of the type Aωs at high frequencies.