Polymer electrolytes composed of an acrylonitrile and butyl acrylate copolymer poly(AN-co-BuA) with addition of LiN(CF3SO2)2 (LiTFSI) or LiI and LiTFSI salt mixture are studied by impedance spectroscopy, DSC, Raman spectroscopy, X-ray diffraction, SEM and TEM. Impedance study shows that the ionic conductivity of the electrolytes containing LiTFSI is strongly dependent on the salt content and transition from “salt-in-polymer” to “polymer-in-salt” regime is observed at high salt content. Gradual changes of physical properties of the studied polymer electrolytes are observed in the course of their prolonged storage under argon atmosphere. These include the increase of glass transition temperature and decrease of ionic conductivity. In order to study the effects of this ageing process, measurements on samples of electrolyte films were repeated after several months. Precipitation of salt, which occurred at the nanometer length scale is observed with the aid of electron microscopy in electrolytes containing more than 84wt.% of salt. Crystalline salt is not observed in electrolytes with lower amount of salt – however, the results indicate the structural changes of salt aggregates, which strongly influence transport of ions through the electrolyte. For preparation of electrolytes with mixed LiTFSI and LiI salts, a mixture of salts (16wt.% LiI, 84wt.% LiTFSI) is used, which exhibits the lowest melting temperature. The electrolyte comprising poly(AN-co-BuA) and 65wt.% of the salt mixture exhibits high ionic conductivity and turns out to be more stable than electrolytes comprising only LiTFSI salt.