Novel sulfur-rich polymer composites were prepared from the commercial polysulfide rubber through facile vulcanization methods and were firstly used as cathode material for lithium/sulfur batteries. The sulfur enriched in the composites includes three parts, the first part was inserted into the main chains of the polysulfide rubber, the second part formed insoluble polysulfide (-S-n-)through self-polymerization and the third part was trapped inside the network of the above two polymer chains. The obtained sulfur-rich polymer composites have high sulfur content over 80%. Compared with the pure sulfur electrode, the composites showed better cycle stability and coulomb efficiency. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.