Charge–discharge properties of a new type of all solid-state lithium cell are presented, which comprises a conductive nano-sulfur composite (NSC) cathode, composite polymer electrolyte based on poly(ethylene oxide), LiN(CF3SO2)2 and nano-sized TiO2 filler and lithium anode. The cell exhibits high discharge capacity up to 600mAhg−1 (referred to the NSC active material, EO/Li=8 for polymer electrolyte) at the second cycle and about 385mAhg−1 at the 40th cycle at operation temperature of 70°C. The electrochemical characteristics of the nano-composite polymer electrolyte, related to the performance of cells, are also examined in detail.