Rechargeable　lithium–sulfur　(Li–S)　batteries　have　received　ever-increasing　attention　owing　to　their　ultrahigh　theoretical　energy　density,　low　cost,　and　environmental　friendliness.　However,　their　practical　application　is　critically　plagued　by　the　sluggish　reaction　kinetics,　shuttling　of　soluble　polysulfide　intermediates,　and　uncontrollable　growth　of　Li　dendrites.　Herein,　a　bimetallic　telluride　electrocatalyst　with　dense　heterointerfaces　and　rich　defects　embedded　in　hollow　carbon　polyhedron　bunches　(N⊂CoTe1-x/ZnTe1-y@NC,　abbreviated　as　NCZTC)　is　rationally　designed　to　simultaneously　address　the　S　cathode　and　Li　anode　problems.　Both　experimental　and　computational　results　substitute　the　integration　of　dense　heterointerfaces　and　rich　defects　can　synergistically　modulate　the　electronic　structure,　enhance　the　electrical　conductivity,　promote　the　Li+　transportation,　strengthen　the　polysulfides　adsorption　and　improve　the　catalytic　activity,　thereby　significantly　accelerating　the　redox　conversion　kinetics　and　prevent　the　dendrite　growth.　Consequently,　Li–S　batteries　with　NCZTC-modified　separators　demonstrate　excellent　electrochemical　performance　including　high　specific　discharge　capacity,　remarkable　rate　capability,　good　long-term　cycling　stability,　and　competitive　areal　capacity　even　at　high　sulfur　loading　and　lean　electrolyte　conditions.　This　study　not　only　provides　valuable　guidance　for　designing　efficient　sulfur　electrocatalysts　with　transition　metal　tellurides　but　also　emphasizes　the　importance　of　heterostructure　design　and　defect　engineering　for　high-performance　Li–S　batteries.　©　2024　Wiley-VCH　GmbH.