In this paper the application of completely new generation imidazole-derived salts in a model polymer electrolyte is described. As a polymer matrix. two types of liquid low molecular weight PEO analogues e.g. dimethyl ether of poly(ethylene glycol) of 500 g mol(-1) average molar mass (PEGDME500) and methyl ether of poly(ethylene glycol) of 350 g mol(-1) average molar mass (PEGME350) were used. Room temperature conductivities measured by electrochemical impedance spectroscopy were found to be as high as 10(-3)-10(-4) S cm(-1) in the 0.1-1 mol dm(-3) range of salt concentrations. Li+ transference numbers higher than 0.5 were measured and calculated using the Bruce-Vincent method. For a complete electrochemical characterization the interphase resistance stability over time was carefully monitored for a period of 30 clays. Structural analysis and interactions between electrolyte components were done by Raman spectroscopy. Fuoss-Kraus semiempirical method was applied for estimation of free ions and ionic agglomerates showing that fraction of ionic agglomerates for salt concentration of 0.1-1 mol dm(-3) is much lower than in electrolytes containing LiClO4 in corresponding concentrations. (C) 2009 Elsevier B.V. All rights reserved.