The　Li-S　battery　has　garnered　widespread　attention　as　an　intriguing　new　energy　storage　equipment　due　to　its　remarkable　energy　density　and　low　cost.　Nevertheless,　the　infamous　shuttle　effect　seriously　hinders　the　commercialization　process.　In　order　to　address　this　issue,　this　study　rationally　synthesizes　the　composites　comprising　Keggin-type　polyoxometalate　and　Co　nanoparticles,　which　are　then　coated　on　a　pristine　polypropylene　separator.　The　modified　separator　can　greatly　inhibit　lithium　polysulfide　shuttling,　thereby　leading　to　a　greatly　improved　electrochemical　performance.　At　the　first　cycle,　the　fabricated　Li-S　battery　exhibits　a　specific　discharge　capacity　of　1335.7　mA　h　g-1,　surpassing　the　938.7　mA　h　g-1　capacity　of　an　unmodified　separator.　At　a　current　density　of　1C,　the　initial　reversible　discharge　capacity　reaches　988.2　mA　h　g-1,　and　even　after　500　cycles,　it　still　retains　a　remaining　capacity　of　664.2　mA　h　g-1,　with　a　capacity　decay　rate　of　0.066%　per　cycle.　Even　at　a　high　sulfur　loading　of　4.2　mg　cm-2,　the　device　displays　a　remarkable　initial　discharge　capacity　of　1158.2　mA　h　g-1,　with　a　remaining　capacity　of　952.7　mA　h　g-1　after　70　cycles　(0.1C).　This　significant　performance　enhancement　could　be　ascribed　to　the　synergistic　effect　of　PMo12/Co-NCe,　which　exhibits　greatly　decreased　electron　transfer　resistance　and　contact　angle　to　the　electrolyte,　facilitating　the　rapid　transport　of　Li-ion　and　kinetics.　Meanwhile,　the　severe　shuttle　effect　is　alleviated　effectively　by　combining　the　strong　catalytic　activity　of　PMo12　and　Co　nanoparticles　with　long-chain　polysulfides.　©　2024　American　Chemical　Society.