The redox system of ceric ammonium nitrate (Ce4+) and alpha,pi-dihydroxy polydimethylsiloxane (DH.PDMS) was used to polymerize N-vinyl carbazole (NVCz) to produce poly(N-vinylcarbazole)-b-alpha,pi-dihydroxy polydimethylsiloxane(PNVCz-b-DH.PDMS). The ratio of NVCz/ceric salt/DH.PDMS has an important effect on the properties of formed copolymers. White insulating PNVCz-b-PDMS copolymers with high fluorescence intensity are produced if the ratio of ceric salt/ NVCz is below 0.2. Green conductive PNVCz-b-PDMS copolymers are produced if this ratio is well above 0.2. The concentration and the type of DH.PDMS affected the polymerization yield. PNVCz-b-DH.PDMS copolymers were also prepared by electroinduced polymerization in the presence of catalytic amount of Cc (4+) in a divided electrochemical cell where Ce3+ is readily oxidized to Ce4+ at the anode. White insulating PNVCz-b-DH.PDMS copolymers show higher contact angle value and lower Tg values than of white poly(N-vinyl carbazole) (PNVCz).