Abstract: Conjugated polymers have attracted much interest in recent years due the many possibilities for their applications in opto-electronics and as non-linear optical materials. Synthetic efforts have been made, on the hand, to improve the properties of well-known oligomers and conjugated polymers and on the other, to prepare new polymers, containing original chain units, from a variety of unsaturated monomers. In this paper we present a selective synthesis of conjugated materials based on thiophene by oxidative polymerization of various silyl monomers. The high sensitivity of the silicon atom offers new synthetic route. As shown by GPC, IR, Raman and photoluminescence criteria, Silicon activates the selective coupling of unsaturated monomers, leading to highly conjugated polymers with improved properties for specific applications.