A series of poly(ferrocenylsilanes) (PFS) with different molecular weight have been prepared via the thermal ring-opening polymerization of the corresponding monomers. The electrochemical behavior of poly(ferrocenyldimethylsilane) (PFDMS) and poly(ferrocenylmethylphenylsilane) (PIMPS) in solutions were investigated by cyclic voltammetry (CV). It was found that PFS could be adsorbed and electrodeposited on the Pt electrode surface, and the electroactive multilayer films formed on the Pt electrode surface influenced the shape of the voltammogram. The redox potential varied with the molecular weight slightly, and Delta E-1/2, became smaller with the increase in molecular weight. (c) 2006 Wiley Periodicals, Inc.