Polymer electrolytes were prepared from thermoplastic polyurethane with addition of mixture of ionic liquid N-ethyl(methylether)-N-methylpyrrolidinium trifluoromethanesulfonimmide (PYRA12O1TFSI), lithium bis(trifluoromethanesulfoneimide) salt and propylene carbonate. The electrolytes characterization was performed by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The electrical properties were investigated in detail by impedance spectroscopy with the aid of equivalent circuit fitting of the impedance spectra. A model describing temperature evolution of ionic conductivity and the properties of electrolyte/blocking electrode interface was developed. The electrochemical stability of the electrolytes was studied by linear voltammetry. Our results indicate that the studied electrolytes have good self-standing characteristics, and also a sufficient level of thermal stability and a fairly good electrochemical window. The ionic conductivity increases with increasing amount of mixture, and the character of temperature dependence of conductivity indicates decoupling of ion transport from polymer matrix. For studied system, the highest value of ionic conductivity measured at room temperature was 10−4 Scm−1.