Electrolytes based on star-branched poly(ethylene oxide) with lithium bis(trifluoromethanesulfone)imide LiTFSI and lithium iodide salts were prepared by casting from solution. The electrical properties of electrolytes subjected to various heating and cooling runs were studied by impedance spectroscopy and impedance spectroscopy simultaneous with optical microscope observation. Differential scanning calorimetry was used for additional characterization. The results indicate that in electrolytes with high content of salt, values of ionic conductivity comparable to that of dilute electrolytes can be achieved. Moreover, electrolytes with high amount of salt seem to show weaker temperature dependence of conductivity. Promising results in terms of ionic conductivity were obtained for mixture of LiTESI and lithium iodide. A few problems which may decrease the performance of studied system as a solid electrolyte were also identified, from which changes of physical properties of samples subjected to thermal cycles and aging seem to be the most important ones. (C) 2010 Elsevier B.V. All rights reserved.