Three newly prepared lithium superacid salts of the type C n F 2 n + 1 SO 3 Li (where n is 4, 8 and 10) and CF 3 SO 3 Li and (CF 3 SO 2 ) 2 NLi were used as salts in polyethylene oxide (PEO) electrolytes. Our conductivity data shows that among the salts investigated PEO electrolytes containing (CF 3 SO 2 ) 2 NLi gave the highest conductivity followed by C 4 F 9 SO 3 Li and C 3 F 1 7 SO 3 Li. PEO electrolytes containing C 1 0 F 2 1 SO 3 Li and CF 3 SO 3 Li showed a lower conductivity at room temperature than the rest. Experimental Li-TiS 2 polymer cells containing either PEO-C 4 F 9 SO 3 Li or PEO-(CF 3 SO 2 ) 2 NLi as electrolyte were fabricated and tested for cycle life performance. No significant loss in capacity was observed even after 50 to 100 cycles.