Lithium–sulfur　batteries　(LSBs)　are　feasible　candidates　for　the　next　generation　of　energy　storage　devices,　but　the　shuttle　effect　of　lithium　polysulfides　(LiPSs)　and　the　poor　electrical　conductivity　of　sulfur　and　lithium　sulfides　limit　their　application.　Herein,　a　sulfur　host　based　on　nitrogen-doped　carbon　(NC)　coated　with　small　amount　of　a　transition　metal　telluride　(TMT)　catalyst　is　proposed　to　overcome　these　limitations.　The　properties　of　the　sulfur　redox　catalyst　are　tuned　by　adjusting　the　anion　vacancy　concentration　and　engineering　a　ZnTe/CoTe2　heterostructures.　Theoretical　calculations　and　experimental　data　demonstrate　that　tellurium　vacancies　enhance　the　adsorption　of　LiPSs,　while　the　formed　TMT/TMT　and　TMT/C　heterostructures　as　well　as　the　overall　architecture　of　the　composite　simultaneously　provide　high　Li+　diffusion　and　fast　electron　transport.　As　a　result,　v-ZnTe/CoTe2@NC/S　sulfur　cathodes　show　excellent　initial　capacities　up　to　1608　mA　h　g−1　at　0.1C　and　stable　cycling　with　an　average　capacity　decay　rate　of　0.022%　per　cycle　at　1C　during　500　cycles.　Even　at　a　high　sulfur　loading　of　5.4　mg　cm–2,　a　high　capacity　of　1273　mA　h　g−1　at　0.1C　is　retained,　and　when　reducing　the　electrolyte　to　7.5　µL　mg−1,　v-ZnTe/CoTe2@NC/S　still　maintains　a　capacity　of　890.8　mA　h　g−1　after　100　cycles　at　0.1C.　©　2023　Wiley-VCH　GmbH.