The formation of a family of silicon- and siloxane-bridged multiferrocenyl derivatives carrying different functional groups attached to silicon, including Fc₂(CH₃)₃C(CH₂)₂SiCHCH₂ (5), Fc₂(CH₂CH–O)SiCHCH₂ (6), Fc₂(OH)SiCHCH₂ (7), Fc₂(CH₂CH–O)Si–O–Si(O–CHCH₂)Fc₂ (8) and Fc₂(CH₂CH–O)Si–O–SiFc₃ (9) is described. Silyl vinyl ether molecules 6, 8 and 9 and the heteroleptic vinylsilane 5 resulted from the competing metathesis reaction of lithioferrocene (FcLi), CH₂CH–OLi or (CH₃)₃C(CH₂)₂Li with the corresponding multifunctional chlorosilane, Cl₃SiCHCH₂ or Cl₃Si–O–SiCl₃. The last two organolithium species have been likely formed in situ by fragmentation of the tetrahydrofuran solvent. Diferrocenylvinyloxyvinylsilane 6 is noteworthy since it represents a rare example of a redox-active silyl mononomer in which two different CC polymerisable groups are directly connected to silicon. The molecular structures of the silicon-containing multiferrocenyl species 5, 6, 8 and 9 have been investigated by single-crystal X-ray diffraction studies, demonstrating the capture and storage processes of two ring fragments resulting from the cleavage of cyclic THF in redox-active and stable crystalline organometallic compounds. From electrochemical studies we found that by changing the anion of the supporting electrolyte from [PF₆]⁻ to [B(C₆F₅)₄]⁻, the redox behaviour of tetrametallic disiloxane 8 can be switched from a poorly resolved multistep redox process to four consecutive well-separated one-electron oxidations, corresponding to the sequential oxidation of the four ferrocenyl moieties.