A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface-confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces, The precursor FRG is synthesized by the application of a facile and novel method for the oxidation of statically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRO synthesized is characterized by 1H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X-ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc.