The polymer-salt complex with high molecular weight poly(vinyl chloride) (PVC) as the host polymer and lithium sulphate (Li(2)SO(4)) as the dopant salt are constructed in the form of thin film. Ionic conductivity studies in the temperature range of 303-373 K are performed for polymer complexes with 75% and 85% PVC. Arrhenius and Vogel-Tamman-Fulcher (VTF) behaviour was observed before and after the T(g) of polymer, respectively. Dielectric constant and electrical modulus were analyzed and it was concluded that the films had ion conducting potential. Fourier transform infrared (FTIR) study confirmed that complexation occurred between PVC and Li(2)SO(4). (C) 2008 Elsevier B.V. All rights reserved.