Electropolymerization can be used to produce uniform and pin-hole free coatings on surfaces of complex shapes, due to the intrinsic characteristic of the process. In this article, the electrocopolymerization behavior of 4-carboxyphenyl maleimide (4CPMI) with styrene onto a steel surface is reported. The polymerization mechanism is by free radical, as might be expected for an aqueous reaction environment. Experimental results suggest that initially a charge transfer complex forms between styrene and 4CPMI, which is much more reactive than either of the two monomers. Alternating copolymers are always obtained at low conversion, even with significant changes in the monomer feed compositions. Because of the incorporation of rigid imide rings into the copolymer backbone, the coating formed has very good thermal properties and is thus a potential candidate for high-temperature applications. Furthermore, the copolymer dielectric constant is comparable to that of commercial polyimides, making it attractive for use in electrical and electronic insulation applications.