Novel vinylferrocenyl-functionalized cyclic and linear polysiloxanes [MeSi{C(Fc)CH2}O]4 (1) and (Me3SiO)(MeSi{C(Fc)CH2}O) n (SiMe3) (n ≈ 35) (3) (Fc = (η5-C5H4)Fe(η5-C5H5) have been synthesized by hydrosilylation reactions of the heterometallic compound Co2(CO)6(μ,η2-HCCFc) with the Si–H-functionalized polysiloxane frameworks [MeSiHO]4 and (Me3SiO)(MeSiHO) n (SiMe3). The solution electrochemical behavior of polysiloxanes 1 and 3 has been investigated and showed that all the vinylferrocenyl units present in the molecules are electrochemically independent. Both neutral tetrametallic cyclotetrasiloxane 1 and polysiloxane 3 become insoluble upon complete oxidation to the corresponding polycationic species, yielding electroactive films on platinum electrodes. In addition, stable electrode surfaces modified with the polyvinylferrocenylsiloxane 3 have been prepared and electrochemically characterized. The well-defined and persistent redox waves of electrodes coated with the polyvinylferrocenylsiloxane films are characteristic of electrochemically stable, surface-confined reversible redox couples.