The electrochemical behavior of three organic bulky salts-(CF3SO2)(2)NLi, (CF3SO2)(2)CHLi and (CF3SO2)(3)CLi-was investigated in an amorphous cross-linked poly(oxyethylene). The best conductivities and the lowest cationic transport numbers were found for the imide salt. Particular attention was paid to the electrochemical stability of (CF3SO2)(2)CHLi in liquid and polymer electrolytes. Compared with (CF3SO2)(2)NLi, (CF3SO2)(2)CHLi was found to have a narrower stability window, both in reduction and in oxidation.