Quaternary polymer electrolyte (PE) based on poly(acrylonitrile) (PAN), 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid (EMImBF4), sulfolane (TMS) and lithium hexafluorophosphate salt (LiPF6) (PAN-EMImBF4-sulfolane-LIPF6) was prepared by the casting technique. Obtained PE films of ca. 0.2–0.3 mm in thickness showed good mechanical properties. They were examined using scanning electron microscopy (SEM), thermogravimetry (TGA, DSC), the flammability test, electrochemical impedance spectroscopy (EIS) and galvanostatic charging/discharging. SEM images revealed a structure consisting of a polymer network (PAN) and space probably occupied by the liquid phase (LiPF6 + EMImBF4 + sulfolane). The polymer electrolyte in contact with an outer flame source did not ignite; it rather underwent decomposition without the formation of flammable products. Room temperature specific conductivity was ca. 2.5 mS cm−1. The activation energy of the conding process was ca. 9.0 kJ mol−1. Compatibility of the polymer electrolyte with metallic lithium and graphite anodes was tested applying the galvanostatic method. Charge transfer resistance for the C6Li → Li+ + e− anode processes, estimated from EIS curve, was ca. 48 Ω. The graphite anode capacity stabilizes at ca. 350 mAh g−1 after the 30th cycle (20 mA g−1).