The strained sila-[ 1] ferrocenophane monomer Fe(eta-(C5H3Bu)-Bu-t) 2SiPh2 ( 5) was synthesized and polymerized via thermal ring-opening polymerization (ROP) both in the melt and in solution to give the soluble high-molecular-weight polyferrocenylsilane (PFS) [Fe(eta-(C5H3Bu2)-Bu-t)(2)SiPh2](n), 7 (M-n = 5.2 x 10(4)- 1.7 x 10(6) Da, PDI = 1.38-1.99). Both monomer 5 and polymer 7 were structurally characterized by H-1, C-13, and Si-29 NMR spectroscopy and elemental analysis. The electronic structure and electrochemical properties of the monomer 5 and the polymer 7 were investigated by UV-vis spectroscopy and cyclic voltammetry. The oxidation potentials were shifted to more negative values relative to non-methylated or methylated analogues, indicating that the electron-donating effect of the Bu-t group is transmitted to the iron center. Polymer 7 exhibited two reversible redox waves with a redox coupling, Delta E-1/2, of 0.33 V, which is indicative of appreciable Fe center dot center dot center dot Fe interactions along the polymer backbone. The resiliency of 7 toward the redox processes was probed by measuring the molecular weights before photooxidation or chemical oxidation ( with tetracyanoethylene (TCNE) or tris(4-bromophenyl)ammoniumyl hexachloroantimonate) and after subsequent reduction of the oxidized polymers to the neutral forms by using bis(pentamethylcyclopentadienyl) iron(II). Significantly, unlike the previous studies of oxidized PFS homopolymers, soluble polymeric salts were obtained even for a high degree of oxidation, and these were characterized by UV-vis and IR spectroscopy. GPC measurements demonstrated the excellent redox resiliency of polyferrocenylsilane 7 to redox cycling as no appreciable decline in molecular weight was apparent for degrees of oxidation of up to 50%.