Poly(vinylidene difluoride-co-hexafluoropropylene) (PVdF-HFP) membrane was prepared by electrospinning. The membranes served as host matrices for the preparation of ionic liquid-based polymer electrolytes (ILPEs) by activation with non-volatile, highly thermally stable, and safe room temperature ionic liquid (RTIL) electrolytes; N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py14TFSI) complexed with 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). In this work, the first combination of electrospun PVdF-HFP fiber polymer host and pyrrolidinium-based ionic electrolyte was employed for highly stable lithium batteries. The ILPE exhibited low Li+–TFSI coordination, low crystallinity, high thermal stability, high electrochemical stability, and high ionic conductivity with a maximum of 1.1 × 10−4 S cm−1 at 0 °C. The ILPE exhibited good compatibility with a LiFePO4 electrode on storage and good charge–discharge performance in Li/ILPE/LiFePO4 cells at room temperature, delivering specific capacities of 143 and 115 mA h g−1 at 0.1 and 1 C-rates. The ILPE also exhibited stable cycle properties and have therefore been demonstrated to be suitable for lithium battery applications.