Electrical behavior of PEDOT:PSS films was investigated for potential application as anode in ITO-free flexible organic optoelectronic devices. Current-voltage, capacitance-voltage, capacitance-frequency and contact resistance-bending cycles characteristics were measured at different electrodes architecture, as well as with and without post-deposition treatment procedure. Information about the hole mobility, conduction mechanism and electrical parameters’ stability at defined mechanical loading was extracted. It was found that UV treatment of the polymeric films is favorable for the improvement of the contact resistance and its mechanical stability, but it results in increasing of the interface capacitance. Optimum electrode gap of 6 mm was established, based on the results obtained for the hole mobility and the specific zones of current saturation from the currentvoltage characteristics. Operational voltage of the unipolar type structure PEDOT:PSS/copper was measured to be 3 V.