Three new polymeric aromatic lithium sulfonylimides were used as salts in high molecular weight poly(ethylene oxide) (PEO) electrolytes. Their conductivity and electrochemical stability behaviors were investigated. The electrolytes with lithium poly [4,4'-(hexafluoroisopropylidene)diphenoxy]sulfonylimide (LiPHFIPSI) showed a better conductive performance compared with the other two lithium salts. The best conductivity was obtained for PEO/LiPHFIPSI EO/Li = 16 (1.90 X 10(-4) S/cm at 60degreesC). Thermal analysis indicated that the salts effectively decreased the crystallinity of PEO. Moreover, the electrolytes also had good electrochemical stability and their oxidative potential was to 5.5 V versus Li/Li+.