An unusual electrochemical response is found for oligoalkylthiophene (13T) films in acetonitrile. A pristine 13T film exhibits a stable redox wave in cyclic voltammogram when the anodic potential limit is below 0.6 V, whereas the redox peaks shift clearly to the negative side by ca. 0.1 V once the 13T film experiences a potential beyond 0.7 V. After this electrochemical stimulus is imposed on a pristine 13T film, the absorption and emission spectra change their features. These findings, along with the measurements with varying thicknesses of 13T films, suggest that a pristine 13T film is a mixture of two phases to be oxidized at separate potentials and that one phase can be switched to the other by the potential stimulation. A plausible model proposed for explaining these observations assumes that a key parameter characteristic of the two phases is a conformation of 13T molecules in the solid state and a change in conformation, leading to the shift of the redox potentials and the change of optical properties, is induced by electrochemical generation of bipolarons on the half units of the oligomers in the pristine 13T film.