The chemical redox system of ceric ammonium nitrate(Ce4+) and poly(dimethylsiloxane)s (PDMS) with monohydroxy (MH), dihydroxy (DH), and diamine(DA) chain ends was used to polymerize acrylonitrile (AN) to produce monohydroxy poly(dimethylsiloxane)s-b-polyacrylonitrile (MH.PDMS-b-PAN), dihydroxy poly(dimethylsiloxane)s-b-polyacrylonitrile (DH.PDMS-b-PAN), and a, ?-diamine poly(dimethylsiloxane)s-b-polyacrylonitrile (DA.PDMS-b-PAN) block copolymers. The concentration, reaction time, and the type of poly(dimethylsiloxane) affect the yield and the molecular weight of the copolymers. The ratio of AN/ceric salt/PDMS has remarkably affects the properties of formed copolymers. DH.PDMS-b-PAN copolymers were also prepared by electroinduced polymerization in the presence of catalytic amount of Ce4+ in a divided electrochemical cell where Ce3+ is readily oxidized into Ce4+ at the anode. The products were characterized by Fourier transform infrared spectroscopy, 1H-NMR spectroscopy, DSC, and their surface properties were investigated through contact-angle measurements. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013