Poly(vinyl alcohol) or PVA complexes with lithium bis(oxalato)borate or LiBOB have been prepared by solution casting. X-ray diffraction reveals that the amorphousness of the polymer increased until 40 wt.% LiBOB salt concentration. The increase in amorphousness is accompanied by a decrease in the glass transition temperature, T-g. The diffusion coefficient of lithium ion obtained from cyclic voltammetry (CV) is 1.98 x 10(-8) cm(2) s(-1). From infrared and impedance spectroscopic studies, it is inferred that conductivity is governed by charge carrier density, ionic mobility and diffusion coefficient for PVA incorporated with 10-40 wt.% LiBOB. However, for the sample with equal weight ratio of PVA and LiBOB, ionic mobility and diffusivity have a greater influence over charge carrier density in determining conductivity at room temperature (RT). PVA can solvate a large amount of salt and for the highest conducting composition of 60 wt.% PVA-40 wt.% LiBOB, conductivity extends from 10(-4) S cm(-1) at RT (25 degrees C) to 10(-3) S cm(-1) at 100 degrees C. This sample was tested as an electrolyte in a Li-air cell. (c) 2013 Elsevier Ltd. All rights reserved.