Herein, dielectric studies of solvent-cast poly(vinyl alcohol) (PVA) with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) freestanding films are conducted in the frequency range of 100Hz-1MHz and temperature ranging from 303 to 453K. An insulator to semiconducting transition is observed for PVA/PEDOT:PSS blend above 413K. Existence of two types of conduction mechanism, hopping between nearest neighbor at low-temperature region (303-383K) and free-band conduction at high temperatures (above 413K) within PVA/PEDOT:PSS films under the influence of applied field, is observed and supported by electric moduli formalisms. An increase in dielectric constant and a significant reduction in tan delta values are observed under high temperature and low frequency with the addition of PEDOT:PSS. Greater than 100% Coulombic efficiency and 82% specific capacitance retention at 5000 cycles are observed for 7.5 vol% PEDOT:PSS in PVA working electrode for supercapacitor. Thus, the fabricated films find potential applications in the field of flexible conventional capacitors and as working electrodes for supercapacitor.