An improved procedure for the preparation of trifluorovinylsilanes was established which involved addition of butyllithium to a mixture of chlorosilanes and commercially readily available chlorotrifluoroethylene at− 78 to− 130° C, and the resulting monomer was polymerized with a catalyst such as CsF or (R 2 N) 3 S+ F 2 SiMe 3− to give black metallic polymer which showed conductivity of 10− 9 to 10− 10 Ω− 1 cm− 1.