The electrochemical behaviors of poly(ferrocenyl si lane) (PFS) films in organic solutions were investigated by means of cyclic voltammetry (CV) and electrochemical quartz crystals microbalance (EQCM). The influences of solvent on the electrochemical behavior of the films were discussed. In "good" solvents, the supporting electrolytes dissociated completely, the films were solvent-swollen moderately which provided a favorable condition for the electrolyte ions penetrating through, and the CV behavior of the films exhibited reversible or nearly reversible features. With increasing the carbon chain length of solvent molecule, however, the polarity of solvent reduced, which conduced to decrease the dissociation of electrolyte and the swelling of the polymer film. The efficiency of electrochemical reaction in the film was depressed, and the CV behavior of the film exhibited low reversibility. The solvent effects on the oxidation process of films exhibited more noticeable than the reduction process. The results supported the viewpoint that penetration of the electrolyte anions played an important role on the charge balance and transfer in the films during the CV process. The different electrochemical behaviors of the two PFS films in various organic solutions indicated that molecular structure of polymer had important influence on the electrochemical properties of the PFS. (c) 2007 Published by Elsevier Ltd.