Poly(3-methylthiophene/overoxidized pyrrole) (PMT/OPPy) composites were electrochemically prepared by simultaneous polymerization of 3-methylthiophene and pyrrole, which were added together at a 10:1 concentration ratio into a non-aqueous medium (acetonitrile). The films were characterized by cyclic voltammetry, spectroscopic (FTIR, UV-VIS, and photocurrent) and current-voltage measurements, and with atomic force microscopy (AFM). The PMT/OPPy films exhibited intermediate characteristics than those seen for the homopolymers, OPPy and PMT, but with PMT as the predominant element of the PMT/OPPy composition. Optical, morphological, and electrical properties of the OPPy, PMT, and PMT/OPPy films were compared aiming toward application in optoelectronic devices and sensors.