The cationic rhodium(I) complexes [Rh(1,5-cod)2]A (A = OTf, PF6, 1,5-cod = 1,5-cyclooctadiene) have been shown to exhibit high catalytic activity for the transition metal-mediated ring-opening polymerization (ROP) of silicon-bridged [1]ferrocenophanes (e.g., fcSiMe2 (1a), fc = Fe(η5-C5H4)2), to quantitatively afford high molecular weight (M n > 105) polyferrocenylsilanes (e.g., [fcSiMe2] n (2a)). However, prolonged exposure of the resulting polyferrocene solution to the catalyst resulted in a dramatic molecular weight decline. Transition metal-catalyzed ROP of tetramethyldisilacyclobutane (6) and copolymerization of this species with 1a also proved readily feasible with [Rh(1,5-cod)2]OTf forming high molecular weight polycarbosilane homopolymer (7) (M n = 4.20 × 105 to 1.08 × 106, PDI = 1.39−2.08) and poly(carbosilane-r-ferrocenylsilane) (8) copolymer (M n = 4.63 × 105, PDI = 1.86), respectively. While [Rh(1,5-cod)(dmpe)]PF6 (dmpe = bis(dimethylphosphinoethane)) proved less active as a ROP catalyst, this species represents the first phosphine-ligated catalyst for the ROP of 1a, and moreover, in this case no subsequent depolymerization of the resulting poly(ferrocenyldimethylsilane) (2a) was detected. The cleavage of the polyferrocene backbone in the presence of [Rh(1,5-cod)2]OTf was modeled through the catalytic reaction of Fc2SiMe2 (Fc = Fe(η5-C5H5)(η5-C5H4)) with the rhodium complex (9 mol %), which resulted in Cp−Si bond cleavage affording ferrocene as the sole, isolable product. The presence of 1,5-cod inhibited the catalytic activity of both [Rh(1,5-cod)2]OTf and [Rh(1,5-cod)(dmpe)]PF6, suggesting that elimination of a 1,5-cod ligand is necessary to generate the true active catalytic species. The addition of dmpe effectively arrested the catalytic activity with [Rh(1,5-cod)(dmpe)]PF6; this is presumably a result of the displacement of the 1,5-cod ligand by dmpe, which would generate catalytically inactive [Rh(dmpe)2]PF6.