The electrochemical behavior of three organic bulky salts-(CF 3 SO 2 ) 2 NLi, (CF 3 SO 2 ) 2 CHLi and (CF 3 SO 2 ) 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 (CF 3 SO 2 ) 2 CHLi in liquid and polymer electrolytes. Compared with (CF 3 SO 2 ) 2 NLi, (CF 3 SO 2 ) 2 CHLi was found to have a narrower stability window, both in reduction and in oxidation.