The synthesis of a series of polyferrocenylsilanes (PFSs) containing C=C functionalities in the side-group structure and their subsequent derivatization by hydrosilylation chemistry are described. Hydrosilylation is shown to be an effective postpolymerization functionalization method, particularly in the case of poly(ferrocenylmethylvinylsilane), which can be prepared by photolytic anionic ring-opening polymerization of the corresponding ferrocenophane monomer.