The　development　of　electrocatalysts　with　high　catalytic　activity　is　conducive　to　enhancing　polysulfides　adsorption　and　reducing　activation　energy　of　polysulfides　conversion,　which　can　effectively　reduce　polysulfide　shuttling　in　Li-S　batteries.　Herein,　a　novel　catalyst　NiCo-MoOx/rGO　(rGO　=　reduced　graphene　oxides)　with　ultra-nanometer　scale　and　high　dispersity　is　derived　from　the　Anderson-type　polyoxometalate　precursors,　which　are　electrostatically　assembled　on　the　multilayer　rGO.　The　catalyst　material　possesses　dual　active　sites,　in　which　Ni-doped　MoOx　exhibits　strong　polysulfide　anchoring　ability,　while　Co-doped　MoOx　facilitates　the　polysulfides　conversion　reaction　kinetics,　thus　breaking　the　Sabatier　effect　in　the　conventional　electrocatalytic　process.　In　addition,　the　prepared　NiCo-MoOx/rGO　modified　PP　separator　(NiCo-MoOx/rGO@PP)　can　serve　as　a　physical　barrier　to　further　inhibit　the　polysulfide　shuttling　effect　and　realize　the　rapid　Li+　migration.　The　results　demonstrate　that　Li-S　coin　cell　with　NiCo-MoOx/rGO@PP　separator　shows　excellent　cycling　performance　with　the　discharge　capacity　of　680　mAhg-1　after　600　cycles　at　1　C　and　the　capacity　fading　of　0.064%　per　cycle.　The　rate　performance　is　also　impressive　with　the　remained　capacity　of　640　mAhg-1　after　200　cycles　even　at　4　C.　When　the　sulfur　loading　is　4.0　mgcm-2　and　electrolyte　volume/sulfur　mass　ratio　(E/S)　ratio　is　6.0　mu　Lmg-1,　a　specific　capacity　of　830　mAhg-1　is　achieved　after　200　cycles　with　a　capacity　decay　of　0.049%　per　cycle.　More　importantly,　the　cell　with　NiCo-MoOx/rGO@PP　separator　exhibits　cycling　performance　under　wide　operating　temperature　with　the　reversible　capacities　of　518,　715,　and　915　mAhg-1　after　100　cycles　at　-20,　0,　and　60　degrees　C,　respectively.　This　study　provides　a　new　design　approach　of　highly　efficient　catalysts　for　sulfur　conversion　reaction　in　Li-S　batteries.