We report here the first electrochemical data on substituted silane high polymer films deposited on a Pt electrode. The oxidation peak potentials were measured for a series of substituted silane high polymers. The polymers oxidize irreversibly and produce soluble products which are removed from the electrode. The ease of oxidation of the polymer depends on the substituents, and polymers with the aryl groups attached directly to the silicon backbone are more easily oxidized.