Effect of solution chemistry on the electropolymerization and the electrochemical properties of polypyrrole coatings on aluminum is studied by means of electrochemical techniques, scanning electron microscopy (SEM), and x-ray photoelectron spectroscopy. It is shown that the protection effect of the coating in long-term exposures and when exposed to more concentrated NaCl solutions depends on the chemistry of electropolymerization electrolyte. The results show that nitrate anions passivate the aluminum substrate during the electropolymerization process. The resulting coating is less prone to blistering in a NaCl solution and probably due to its higher electrochemical activity presents a higher anodic protection effect. The galvanic interaction of polypyrrole coating with aluminum in a NaCl solution is directly observed using focused ion beam-assisted SEM.