Uniform and adherent copolymer coating of poly(aniline-co-isoprene) was successfully formed on low-carbon-steel electrodes by potentiostatic electropolymerization. Electropolymerization was performed by using aqueous p-toluene sulfonic acid solution as electrolyte. Applied potential and feed ratios of monomers (aniline and isoprene) were systematically varied and the reactions were done under aqueous conditions. The copolymer coatings were characterized by infrared spectroscopy and the formation of copolymer was confirmed by the presence of aliphatic secondary amine, aromatic secondary amine, and aliphatic CH stretch groups. The electronic structure of the copolymers was further investigated by using UV/Vis absorption spectroscopy. The electrochemistry of the formation of copolymers was studied by using cyclic voltammetry.