Nanocomposite solid polymer electrolyte films based on poly-vinyl alcohol were synthesized using solution cast technique. The effects of electric field on the ionic conductivity were investigated. The addition of nanofillers such as BaTiO3, SrTiO3, Al2O3 and MMT to PVA has been found to increase the DC electrical conductivity of the SPE films. The structural change induced in the sample due to the addition of nanofillers was investigated using DSC and XRD techniques. The XRD and DSC results show that amorphosity of the sample increased as the combination of nanofillers was added to the polymer matrix. The temperature dependence of the DC electrical conductivity was carried out between 298–323 K and varying the electric fields from 0 to 100 Vcm−1. The obtained results reveal that ionic conductivity of the electrolyte film increased non-linearly with electric field. The electric field and temperature-dependent conductivity of the polymer electrolyte films were explained using the mathematical model proposed earlier. The field factor and activation energy for the PVA-based system were evaluated.