This paper reports on the preparation of poly(methyl methacrylate) (PMMA), poly(n-butyl acrylate) (PBA), and polystyrene (PS) brushes at the surface of conducting materials that were modified by the electrochemical reduction of a brominated aryl diazonium salt BF4(-), +N-2-C6H4-CH(CH3)-Br (D1). The grafted organic species -C6H4-CH(CH3)-Br was found to be very effective in initiating atom transfer radical polymerization (ATRP) of vinyl monomers. This novel approach combining diazonium salts and ATRP allowed PMMA, PBA, and PS brushes to be grown from the surface of iron electrodes. The polymer films were characterized in terms of their chemical structure by infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy. Atomic force microscopy studies indicated that the polymer brushes are densely packed. Contact angle measurements of water drops on PS and PMMA brushes were 88.1 ± 2.0 and 70.3 ± 2. 1°, respectively, which is consistent with the published wettability data for the corresponding polymer sheets.