Free-standing, flexible, composite films of poly(vinylidene fluoride)/poly(3,4 ethyelenedioxythiophene):poly(styrelenesulfonate) (PVDF/PEDOT:PSS) were deposited. The films were characterized using Field Emission Scanning Electron Microscopy, X-Ray Diffraction, Raman, and Fourier-transformed infrared spectroscopic studies. Enhancement in the conductivity with an increase in the concentration of the additives was observed. The electrical conductivity of the high resistive PVDF films increased to ∼10−3Scm−1 with the addition of a maximum of 1.7 mL of a 1.3 wt.% aqueous dispersion of PEDOT:PSS. An increase in the conductivity of the films with temperature was observed, indicating semiconducting nature. At room temperature, the conductivity of the composite films was found to be in the range of ∼1.3 × 10−4Scm−1 to ∼7.3 × 10−3 Scm−1. The conductivity of the composite films was found to follow the Mott Variable Range Hopping model of conduction.