The use of sulfur in the next generation Li-ion batteries is currently precluded by its poor cycling stability caused by irreversible Li2S formation and the dissolution of soluble polysulfides in organic electrolytes that leads to parasitic cell reactions. Here, a new C/S cathode material comprising short-chain sulfur species (predominately S-2) confined in carbonaceous subnanometer and the unique charge mechanism for the subnano-entrapped S-2 cathodes are reported. The first charge-discharge cycle of the C/S cathode in the carbonate electrolyte forms a new type of thiocarbonate-like solid electrolyte interphase (SEI). The SEI coated C/S cathode stably delivers approximate to 600 mAh g(-1) capacity over 4020 cycles (0.0014% loss cycle(-1)) at approximate to 100% Coulombic efficiency. Extensive X-ray photoelectron spectroscopy analysis of the discharged cathodes shows a new type of S-2 species and a new carbide-like species simultaneously, and both peaks disappear upon charging. These data suggest a new sulfur redox mechanism involving a separated Li+/S2- ion couple that precludes Li2S compound formation and prevents the dissolution of soluble sulfur anions. This new charge/discharge process leads to remarkable cycling stability and reversibility.