Abstract: The gel polymer electrolyte containing N-propyl, methylpyrrolidinium bis((trifluoromethyl) sulfonyl)imide (PYR13TFSI) with better performance is prepared by radical polymerization method. The interface status between the LiFePO₄ electrode and the electrolyte is character-ized by a scanning electron microscope and X-ray photoelectron spectroscopy (XPS). There is a layer of membrane on the gel electrolyte and perfect shell membranes on the surface of active LiFePO₄ cluster, on the other hand, N and S photoelectron signals are observed in XPS spectra after charge-discharge cycles. The results show that the ionic liquids and unpolymerized methyl methacrylate incorporate into the electrode surface and form the SEI membrane with Li ion and electrons while the gel electrolyte contacts with the electrode. The formation process of the SEI membrane needs at least three cycles, the discharge capac-ity increases as the SEI membrane becomes sufficiently thick, which blocks further electron transfer, and the system may approach steady state. The performance of cell with ionic liquid gel polymer electrolyte is measured at different rate. The cells retain 132 mAh/g at 0.2 C, 128 mAh/g at 0.5 C, and 120 mAh/g at 1.0 C after 30 cycles with charge-discharge efficiency of ca. 98% at every rate.