We propose a novel composite (hybrid) organic/inorganic system that can be prepared as a coating (on 1 mu m level) on glassy carbon and metal electrode substrates. Poly(3,4-ethylenedioxythiophene) or PEDOT based composite coatings were electrodeposited using cyclic voltammetry on glassy carbon and stainless steel substrates in the presence of 4-(pyrrole-1-yl) benzoic acid (PyBA) and phosphododecamolybdic acid (PMo12). The coating growth was facilitated by the addition of polyoxyethylene-10-laurylether (BRIJ10) neutral surfactant at the level of 0.04 mol dm(-1) to improve solubility of the 3,4-ethylenedioxythiophene monomer and to form an aqueous micellear solution in the reaction medium. The fact that carboxylate-containing PyBA units link positively charged PEDOT structures tends to improve overall stability and adherence of composite coatings to stainless steel. The PEDOT/PyBA composite serves as a stable host matrix for large negatively charged polymolybdate inorganic species. Consequently, due to the formation of denser polymeric structures and to the existence of electrostatic repulsion effects, the polyanion-containing composite coatings are capable of largely blocking the access of pitting-causing anions (chlorides) to the surface of stainless steel. Interaction of phosphomolybdate with metal ions, namely with chromium(III) or even iron( Ill) or iron(II) that exist at the stainless steel-composite coating interface, may lead to the formation of insoluble deposits and exhibit overall passivating effect. (C) 2010 Elsevier Ltd. All rights reserved.