The 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) doped polymer films were prepared with Polypyrrole (PPy) and Polyvinyl alcohol (PVA) polymers by solution-casting. The change in structure and chemical composition of samples was identified by XRD and FTIR respectively. The UV-visible spectroscopy demonstrates the optical characteristics and band gap properties of sample. The homogeneous morphology of sample for higher wt% of PTCDA was examined by atomic force microscopy (AFM). The differential scanning calorimetry (DSC) results demonstrate the decrease in melting temperature (Tm) and degree of crystallinity (χc%) of polymeric organic semiconductor. The mechanical property demonstrates the high tensile strength and improved plasticity nature. Impedance spectroscopy was evaluated to determine the conductivity response of polymeric organic semiconductor. The highest DC conductivity (2.08×10-3 S/m) was obtained for 10 wt% of PTCDA at 140 °C. The decrease in activation energy (Ea) represents the non-Debye process and was evaluated from the slope of ln σdc vs. 103/T plot. © 2015 Elsevier Ltd.All rights reserved.