A　better　understanding　of　the　redox　process　of　lithium　polysulfide　(LPS)　on　carbon　surfaces　is　helpful　for　designing　Li/S　batteries　with　better　performance.　The　＂shuttle　mechanism＂　can　explain　the　low　coulomb　efficiency　and　self-discharge　of　a　Li/S　battery,　but　it　cannot　explain　the　fact　that　battery　performance　is　strongly　affected　by　electrolyte　volume　and　sulfur　load.　This　paper　aims　to　reveal　the　main　redox　process　of　LPS　on　the　surface　of　carbon　by　examining　the　cathodic　behavior　with　different　electrolyte　volume　and　sulfur　load.　Scanning　electron　microscopy　(SEM)　images　and　impedance　spectra　of　the　cathode　before　and　after　the　first　discharge　were　compared,　and　it　was　found　that　the　discharge　process　is　the　continuous　dissolution　of　sulfur　composited　with　carbon　into　the　electrolyte　to　form　LPS.　At　the　same　time,　LPS　re-precipitates　sulfur　on　the　surface　of　the　cathode　through　a　disproportionation　reaction　to　form　a　solid　film.　Cyclic　voltammetry　(CV)　curves　showed　that　the　solid　film　passivates　the　electrode,　and　the　electrode　is　activated　only　when　the　potential　is　swept　negatively　and　Li2S　is　generated.　When　a　lean　electrolyte　is　used,　there　is　fluctuation　in　the　CV　curves,　which　proves　that　the　dissolution-reprecipitation　of　sulfur　is　the　main　process　of　the　cathode.　The　discharge-charge　curves　of　cathodes　with　different　sulfur　load　were　compared,　and　it　was　found　that　there　is　wavy　fluctuation　in　the　discharge　curve　when　the　sulfur　load　increases,　which　proves　again　that　the　sulfur　reaction　dominates　the　electrode　process.　[GRAPHICS]　.