Polyaniline/silver (PANI/Ag) nanocomposite was successfully prepared by in-situ polymerization from nanosilver sol using aniline (An) as both dispersant and stabilizer and characterized by FT-IR, XRD SEM, TEM and electrochemical methods, respectively. The results showed that core-shelled composite particles of less than 100 nm were synthesized with PANI as shell formed around a core of silver nanoparticles at higher aniline levels. Compared to pure PANI, PANI/Ag nanocomposites have higher electrical conductivity (65.98 S/cm) and current response and capacitance as well. Potentio dynamic polarization showed the anodic shifting of zero current potential and a lower exchange current density for the PANI/Ag composite. Compared with PANI, the PANI/Ag nanocomposite is a promising candidate for coatings with improved anti-corrosion performance. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013