The linear-dendritic polymer poly(ferrocenyldimethylsilane)-b-poly(benzyl ether) (PFS-PBE) films were prepared and their electrochemical behavior in LiClO4 aqueous electrolyte solutions was investigated with cyclic voltammetry (CV). Reversible CV processes were obtained for PFS27-PBE1, film and irreversible CV processes were obtained for PFS20-PBE2 film in aqueous electrolyte solutions. The kinetic parameters 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 also discussed. (c) 2005 Elsevier B.V. All rights reserved.