Abstract The polymer electrolytes (ion conducting polymers) consist of macromolecules (usually in the form of polyethereal units) that are doped with alkali mental salts. The polymer electrolytes are being used in Li-polymer buttery. It is suggested that conductivity in these systems takes place through two distinct events. The first is associated with the charge migration of ions between coordination sites in the host material, and the second is that the conductivity is generally observed to rise with increasing flexibility of the polymer chains. Rayleigh-Brillouin scattering spectra of molecular liquids will provide mechanical relaxation information in the frequency range from 10^8 to 10^11 Hz. We have carried out the Brillouin scattering study of PEG400/LiCl mixtures to probe its elastic properties. The change in the flexibility of polymer chains at different temperatures, the fraction of free ion, and their interactions with polymer all effect the Brillouin spectrum and the present work suggests the usefulness of this technique as an useful tool to probe the various interactions in polymer electrolytes.