Lithium–sulfur　batteries　(LSBs)　showcase　great　promise　for　large-scale　energy　storage　systems,　however,　their　practical　commercialization　is　seriously　hindered　by　the　sluggish　redox　reaction　kinetics　and　detrimental　shuttle　effect　of　soluble　polysulfides.　Herein,　small　ZnTe1-x　nanoparticles　with　anionic　vacancies　firmly　anchored　on　3D　ordered　macroporous　N-doped　carbon　skeleton　(3DOM-ZnTe1-x@NC)　are　elaborately　constructed　as　a　high-efficiency　electrocatalyst　for　LSBs.　The　ordered　macroporous　carbon　skeleton　not　only　greatly　increases　the　external　surface　area　to　expose　sufficient　active　sites　but　also　facilitates　the　electrolyte　penetration.　Additionally,　the　experimental　studies　combined　with　theoretical　calculations　confirm　the　presence　of　Te　vacancies　optimizes　the　electronic　structure　to　enhance　the　intrinsic　catalytic　activity　and　chemical　absorption.　Consequently,　LSBs　assembled　with　the　3DOM-ZnTe1-x@NC　modified　separators　exhibit　high　specific　discharge　capacity,　as　well　as　superior　rate　performance　and　good　long-term　cycling　stability.　Even　under　a　high　sulfur　loading　of　6.5　mg　cm−2　and　lean　electrolyte,　an　impressive　areal　capacity　of　5.28　mAh　cm−2　is　achieved　at　0.1 C　after　100　cycles.　More　significantly,　the　3DOM-ZnTe1-x@NC　based　pouch　cells　are　also　fabricated　to　demonstrate　its　potential　for　practical　applications.　This　work　highlights　that　the　rational　combination　of　3DOM　architecture　and　vacancy　engineering　is　important　for　designing　advanced　Li–S　electrocatalysts.　©　2024　Wiley-VCH　GmbH.