A new type of lithium salts, -SO2NLiSO2OCH2(CF2)(n)CH2Om-(LiPP-FASI, where n = 2, 3, 4, 6, and 7), was used as salts in poly(ethylene oxide) (PEO)based solvent-free electrolytes. The conductivity and electrochemical stability behaviors were studied. The results showed the electrolytes almost have a similar conductivity and the PEO-LiPPFASI (n = 3, EO/Li = 10) was the relatively better system under the experiment conditions. Moreover, most systems were found to be oxidatively stable up to 5.5 V versus Li/Li+ and the lithium deposition-stripping process on the electrode was reversible for all the polymer electrolytes.