The characteristics of dip-coated polystyrene–poly(2-cinnamoylethyl methacrylate) (PS n –PCEMA m ) copolymeric coatings on Au wire and sputtered Au (on quartz crystals) electrodes have been investigated using TEM, cyclic voltammetry, mass measurements and ellipsometry. TEM studies of PS 800–PCEMA 600 films, formed from an 86% cyclopentane (CP)/14% THF solvent, without subsequent rinsing, are 70–85 nm thick and are in the form of micelles, ca. 40 nm in diameter. The coverage of Au by the PS n –PCEMA m micellar coating, established using cyclic voltammetry in pH 7 solutions, increases with deposition time and with the concentration of PS n –PCEMA m in the deposition solution. Also, the coverage is higher on smooth sputtered Au versus Au wires and for copolymers containing the greatest number of styrene units, independent of the ratio of the number of PS to PCEMA units. Rinsing the PS n –PCEMA m coating with the block selective solvent after coating deposition rapidly decreases the coating density, thickness and surface coverage. An interesting feature of these coatings is that the copolymer (likely the PCEMA block) promotes the formation of a hydrous Au β-oxide film at anomolously low potentials.