The electronic properties of electropolymerized films of the 3,4-ethylenedioxy-substituted conducting polymers (CP) poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxypyrrole) (PEDOP) and poly-(3,4-ethylenedioxyselenophene) (PEDOS) have been investigated, along with their electrocatalytic activity toward 2,5-dimercapto-1,3,4-thiadiazole (DMcT). For the electropolymerized films, the conductivity onset potential was most negative for PEDOP (-1.50 V), followed by PEDOS (-1.35 V) and with PEDOT possessing the most positive onset (-1.15 V). The heterogeneous charge transfer rate constant for DMcT in solution at polymer-film-modified glassy carbon electrodes (GCEs) was studied. It was found that compared to PEDOP, both PEDOS and PEDOT performed better as electrocatalysts, with PEDOS having a heterogeneous charge transfer rate constant of 1.8 x 10(-3) cm/s. The film morphology of the electropolymerized films was investigated via SEM, and some film characteristics could be correlated with electrocatalytic activity. The potential use of CP/DMcT composites for lithium ion batteries (LIBs) is discussed.