Polyaniline coatings were electrodeposited from an oxalic acid solution onto iron and their electrochemical activity and corrosion protection properties studied as a function of pH. It was found that the coating (emeraldine salt) had a limited effect on the corrosion protection of iron in acidic solutions. However, in an alkaline borate solution, where the conducting polyaniline was converted to the emeraldine base, the coating had a clear beneficial effect on the local breakdown of iron by chloride anions; much higher pitting potentials were recorded following a 2 h immersion period for the polyaniline-coated substrate relative to the uncoated electrode. Relatively small anions, such as acetates, nitrates and borates, were transported readily across the polymer interface. However, the emeraldine base inhibited the transport of the much larger ethylenediamine tetraacetate (EDTA) species to the iron interface, preventing complexation of the iron by EDTA.