In this work, a new approach to vulcanize commercial poly(vinyl chloride) (PVC) at room temperature and in a relatively short time (4 h) by using elemental sulfur and an initiator such as Na2S.9H(2)O is reported. The obtained crosslinked polymer contains polysulfide linkages that facilitate recycling/self-healing through dynamic S-S linkages. It is shown that PVC-polysulfide networks could be reprocessed at 180 degrees C for three times. The thermal and spectral characterizations of the polymers before and after recycling are performed via FT-IR, DSC, and TGA analyses. The potential use of the sulfur rich PVC-polysulfide system as cathode material for Li-S battery application is also investigated and the first discharge capacity is found to be around 610 mAh g(-1) that later faded rapidly.