Gel polymer electrolytes containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and a small amount of additive (vinylene carbonate, fluoroethylene carbonate, and ethylene carbonate) are prepared, and their electrochemical properties are investigated. The cathodic limit of the gel polymer electrolytes can be extended to 0V vs. Li by the formation of a protective solid electrolyte interphase on the electrode surface. Using these gel polymer electrolytes, lithium metal polymer cells composed of a lithium anode and a LiNi1/3Co1/3Mn1/3O2 cathode are assembled, and their cycling performances are evaluated at room temperature. The cells show good cycling performance, comparable to that of a cell assembled with gel polymer electrolyte containing standard liquid electrolyte (1.0M LiPF6 in ethylene carbonate/diethylene carbonate). Flammability tests and differential scanning calorimetry studies show that the presence of the ionic liquid in the gel polymer electrolyte considerably improves the safety and thermal stability of the cells.