New gel polymer electrolytes containing 1-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide (BMPyTFSI) ionic liquid are prepared by solution casting method. Thermal and electrochemical properties have been determined for these gel polymer electrolytes. The addition of BMPyTFSI to the P(EO)20LiTFSI electrolyte results in an increase of the ionic conductivity, and at high BMPyTFSI concentration (BMPy+/Li+ =1.0), the ionic conductivity reaches the value of 6.9×10−4 S/cm at 40°C. The lithium ion transference numbers obtained from polarization measurements at 40°C were found to decrease as the amount of BMPyTFSI increased. However, the lithium ionic conductivity increased with the content of BMPyTFSI. The electrochemical stability and interfacial stability for these gel polymer electrolytes were significantly improved due to the incorporation of BMPyTFSI.