Solvent-free P(EO)20LiTFSI+PYR14TFSI polymer electrolyte films with PYR14 +/Li+ mole ratios ranging from 0.96 to 3.22 were prepared by hot-pressing mixtures composed of PEO, LiTFSI and PYR14TFSI of selected stoichiometries. The PYR14TFSI room temperature ionic liquid (RTIL) is homogeneously incorporated into the P(EO)20LiTFSI membrane without phase separation. For a PYR14 +/Li+ mole ratio of 3.22, the ionic conductivity was about 2×10−4 S/cm at 20°C, i.e., more than one order of magnitude higher than that of the RTIL-free electrolyte. The electrochemical stability window of the polymer electrolyte containing the RTIL was about 6V (versus Ag/Ag+). Li/V2O5 cells with the polymer electrolyte (PYR14 +/Li+ =1.92) showed a 60% capacity retention after 80 cycles at 40°C (the initial capacity was 210mAh/g). Li/V2O5 cells (PYR14 +/Li+ =1.28) held at 30°C delivered about 93mAh/g (at 0.057mA/cm2), which corresponds to approximately 34% utilization of the active material. These results suggest that the incorporation of the RTILs into PEO-based polymer electrolytes is very promising for the future realization of solid-state lithium metal polymer batteries operating near ambient temperatures.