Lithium-ion battery holds great promises for future energy storage purpose. However, traditional Lithium-ion battery uses liquid organic electrolytes which is flammable and leads to safety problems. In this work, we present a highly ion conducting membrane which is discovered by doping a nonvolatile conducting medium, ionic liquids (ILs) in solid polymer electrolytes (SPEs) prepared under external electric field(EF)  poling. The poling created aligned morphology in PVDF-HFP and PMMA blending system yield the long-range ordered but nearly totally amorphous domains where nonflammable ionic liquids is inter-dispersed to display unusually high Li⁺ transport with room temperature conductivity reaching over 10^-3S/cm. The highest conductivity of 7.53x10^-3 S/cm is observed for polymer electrolyte containing PMMA/PVDF-HFP (50/50 wt%, eV8E2L). The alignment by the external electric field not only altered the interaction between polymer components which suppressed PVDF-HPF crystallinity in the SPEs, it also improves mechanical strength of the membrane .The coin cell (R2032) using eV8E2L as the SPEs and LiFePO₄ cathode shows fair half-cell performance and durable cycle stability. Under 0.1C-rate the half-cell displayed consistent discharge capacity of 140 mAh/g , without apparent capacity decay.