The electrochemical behavior of high-molecular-weight poly(ferrocenyldimethylsilane) films and poly(ferrocenylmethylphenylsilane) films, which contained about 2.8 x 10(-6) mol cm(-2) ferrocene sites in eight kinds of aqueous electrolyte solutions, was investigated with cyclic voltammetry (CV). In some aqueous electrolyte solutions, the CV peak currents diminished gradually with an increase in the scanning times, whereas in other aqueous electrolyte solutions, stable and repeated cyclic voltammograrns were obtained. The polymer films were poor-solvent-swollen in aqueous electrolyte solutions, and this resulted in a high resistivity of mass transfer and a slow rate of electrode reaction; therefore; quasireversible or irreversible CV processes were obtained. The kinetic parameters of the film-electrode processes, such as the surface transfer coefficient, the apparent diffusion coefficient, and the standard rate constant for electron transfer, for the two films in aqueous LiClO4, solutions were measured, and the electrode process mechanism of the films was examined. (C) 2004 Wiley Periodicals, Inc.