Reaction of dichlorodiferrocenylsilane, Fc2SiCl2 (4) (Fc=(η-C5H4)Fe(η-C5H5)), with dilithioferrocene fcLi2·TMEDA (fc=(η-C5H4)2Fe, TMEDA=N,N,N,N-tetramethylethylenediamine) afforded the novel trimetallic [1]silaferrocenophane 5, fcSiFc2, in 77% yield. A single crystal X-ray diffraction study of ferrocenophane 5 showed the presence of significant disorder but revealed that the molecule possesses a highly strained structure where the tilt-angle between the planes of the cyclopentadienyl rings of the ferrocenophane is 20–22°, typical of strained silicon-bridged [1]ferrocenophanes. The Fe⋯Fe distances in 5 are 5.434, 5.537, and 5.687 Å, and metal–metal interactions are evident as redox coupling was detected in the cyclic voltammogram of this species. Differential pulse voltammetry resolved three oxidation waves at 0, 0.22, and 0.45 V relative to the ferrocene/ferrocenium couple. Mössbauer spectroscopy proved useful in corroborating the structure of 5, as the two distinct Fe environments present were readily resolved (δ=0.424(5) mm s−1, d, ΔEq=2.242(5) mm s−1, 2 Fe; δ=0.414(5) mm s−1, d, ΔEq=1.930(5) mm s−1, 1 Fe). Further characterization of 5 by IR and Raman spectroscopy was also undertaken. Ring-opening addition of HCl across a strained Si–C bond of 5 afforded chlorotriferrocenylsilane, Fc3SiCl (6), in 81% yield. Subsequent hydrolysis of 6 afforded a silanol Fc3SiOH (7) with three ferrocenyl substituents. Single crystal X-ray diffraction of 7 revealed that the compound crystallizes as hydrogen-bonded dimers. When heated, 5 was found to undergo thermal ring-opening polymerization (ROP) to afford cyclic oligomeric species [fcSiFc2]x (9x, x=2 or 3) and an insoluble polymeric material [fcSiFc2]n (8). Copolymers 10 were obtained when 5 was heated in the presence of dimethyl[1]silaferrocenophane, fcSiMe2 (1a)