Electrochemical synthesis of polypyrrole (PPy)/polyhedral oligomeric silsesquioxane (POSS) nanocom-posite on copper is studied using cyclic voltammetry technique in aqueous sodium benzoate solution. Theresulting PPy/Cu and PPy/POSS/Cu films were characterized by Fourier transform infrared spectroscopy(FTIR) and scanning electron microscopy (SEM) analysis. The performance of PPy and PPy/POSS nanocom-posite as protective coatings against corrosion of Cu in 3.5% NaCl solution is assessed by potentiodynamicpolarization technique and electrochemical impedance spectroscopy (EIS). The corrosion potential forPPy/POSS/Cu is positively shifts by 0.071 V in comparison with uncoated copper. The corrosion currentdensity is found to be 24.08, 7.23, and 2.101 A/cm2for uncoated Cu, PPy coated Cu and PPy/POSS coatedCu, respectively. The results showed that by adding the POSS nanostructures within PPy matrix, thecurrent density of the monomer oxidation decreased, significantly. The EIS studies indicated that thecharge transfer resistance increases with the presence of PPy/POSS and accordingly, protection of copperimproved against corrosion action.