In this paper, the feasibility for investigations of the redox behaviour of electrochemically prepared polybithiophene film electrodes in contact with aqueous solutions is demonstrated. The characterization of semiconductor properties of the polymer is demonstrated by Electrochemical Impedance Spectroscopy (EIS) and Photocurrent measurements in dependence of the electrode potential. EIS was employed to determine the polymer resistance and the capacitance as a function of the potential, The resulting Mott-Schottky plot of the polymer capacitance describes the reduced (neutral) polymer as a p-type semiconductor with a flat band potential of about 600 mV (vs SCE). Photocurrent measurements confirmed these results.