Poly(vinyl chloride) (PVC)-LiAsF6 polymer electrolytes plasticized with dibutyl phthalate in different mole ratios have been studied by means of X-ray diffraction (XRD), infrared spectroscopy (IR) and a.c. impedance spectroscopy. The complexation has been confirmed from XRD and IR studies. A maximum room temperature conductivity (3.938×10−5 S cm−1) has been observed for PVC: LiAsF6: DBP (10:5:85 mol%) complex. The log σ vs. 1/T plots (σ=electrical conductivity; T=temperature) show Arrhenius behaviour. The activation energy is estimated and the results are discussed.