This work concerns the design, the synthesis, and the characterization of the N-butyl-N-ethylpiperidinium N, N-bis(trifluoromethane )sulfonimide (PP24TFSI) ionic liquid (IL). To impart Li-ion transport, a suitable amount of lithium N,N-bis-(trifluoromethane)sulfonimide (LiTFSI) is added to the IL. The Li-IL mixture displays ionic conductivity values on the order of 10(-4) S cm(-1) and an electrochemical stability window in the range of 1.8-4.5 V vs Li+/Li. The voltammetric analysis demonstrates that the cathodic decomposition gives rise to a passivating layer on the surface of the working electrode, which kinetically extends the stability of the Li/IL interface as confirmed by electrochemical impedance spectroscopy measurements. The LiTFSI-PP24TFSI mixture is incorporated in a poly(vinylidene fluoride-co-hexafluoropropylene) matrix to form various electrolyte membranes with different LiTFSI-PP24TFSI contents. The ionic conductivity of all the membranes resembles that of the LiTFSI-IL mixture, suggesting an ionic transport mechanism similar to that of the liquid component. NMR measurements demonstrate a reduction in the mobility of all ions following the addition of LiTFSI to the PP24TFSI IL and when incorporating the mixture into the membrane. Finally, an unexpected but potentially significant enhancement in Li transference number is observed in passing from the liquid to the membrane electrolyte system. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3122885] All rights reserved.