In this present study, a series of polymer electrolyte thin films were synthesized by incorporating different ratios of lithium triflate (LiCF3SO3) in a low molecular weight polyvinyl chloride (PVC) matrix by the solution casting technique. The incorporation of LiCF3SO3 suppressed the high degree of crystallinity in PVC enabling the system to possess an appreciable ionic conductivity. The ionic conductivity of the samples, with different LiCF3SO3 content, was determined by the aid of ac impedance spectroscopy. The highest ionic conductivity of 4.04 10–9 S cm–1 was identified for the composition of PVC: LiCF3SO3 (75:25). Further understanding of the ionic conductivity mechanism was based on temperature-dependent conductivity data which obeyed Arrhenius theory, indicating that the ionic conductivity enhancement was thermally assisted. The possible dipole-dipole interaction between the chemical constituents was confirmed with changes in cage peak, analysed using Fourier transform infrared spectroscopy.