Poly (ethylene oxide) (PEO)-based polymer electrolytes show the prospect in all-solid-state lithium metal batteries; however, they present limitations of low room-temperature ionic conductivity, and interfacial incompatibility with high voltage cathodes. Therefore, a salt engineering of 1, 1, 2, 2, 3, 3-hexafluoropropane-1, 3-disulfonimide lithium salt (LiHFDF)/LiTFSI system was developed in PEO-based electrolyte, demonstrating to effectively regulate Li ion transport and improve the interfacial stability under high voltage. We show, by manipulating the interaction between PEO matrix and TFSI-- HFDF-, the optimized solid-state polymer electrolyte achieves maximum Li+ conduction of 1.24 3 10(-4) S cm( -1 )at 40 degrees C, which is almost 3 times of the baseline. Also, the optimized polymer electrolyte demonstrates outstanding stable cycling in the LiFePO4/Li and LiNi(0.8)Mn0.1Co(0.1)O(2)/Li (3.0-4.4 V, 200 cycles) based all-solid-state lithium batteries at 40 degrees C.