Coatings of poly(2-vinylpyridine) have been formed on mild steel substrates in aqueous medium by electrochemical polymerization of the 2-vinylpyridine monomer. The pH of the solution has been found to be critical for this electropolymerization coating process. At low pH (below 3.5), even with an efficient initiation reaction, the propagation process was impeded and no substantial polymer film was formed. At high pH (above 6.0), only a thin and irregular film formed due to the lack of an effective initiation reaction. Only when the solution pH is in the range of 4 to 5.5 can good quality coatings be formed on mild steel substrates. The detailed effects of the pH on the electropolymerization are discussed in terms of a proposed free radical polymerization mechanism. This research has also resolved the issue of some of the non-reproducible experimental results reported in the literature and confirmed the feasibility of forming poly(2-vinylpyridine) coatings on a mild steel substrate by electropolymerization of the monomer.