A novel thiolane polymer, poly[1,2,4,5-tetrakis(propylthio)benzene] (PTPB), was synthesized by facile oxidative-coupling polymerization, characterized by FT-IR, XPS, XRD, TGA and EA, and tested as cathode active material in rechargeable lithium batteries. The FT-IR, XPS and elemental analysis confirm the occurrence of polymerization and show the existence of C-S-C bonds. The results show that the thiolane polymer has electrochemical activity as cathode material in lithium batteries and thioether bonds may be the centers of the electrode reaction. A maximum specific capacity of 200 mAh g-1was obtained and this agrees roughly with the theoretical prediction. In addition, high voltage efficiency was obtained first time from sulfide polymer.