Films of PVA/PVP blend (50/50) filled with different concentrations of LiBr were prepared. The prepared films were investigated by different techniques. XRD scans demonstrate that complexation between the filler and the blend takes place in the amorphous region. UV-VIS analysis revealed that the values of the optical energies are changed with increase Li-ions content. This indicates that there is a charge transfer complexes arise between the polymer blend and Li-ions. The thermal stability of the product samples has improved after filling LiBr increases, this indicates that the filler acts as a plasticizer. The rise of the conductivity is significant with increased concentration of LiBr, this is means the decrease in the degree of crystallinity and increase in the degree of amorphosity. This suggests the choice of LiBr as filler to improve the electrical conductivity of PVA/PVP. (C) 2009 Elsevier B.V. All rights reserved.