Modulating　the　electronic　configuration　of　the　substrate　to　achieve　the　optimal　chemisorption　toward　polysulfides　(LiPSs)　for　boosting　polysulfide　conversion　is　a　promising　way　to　the　efficient　Li–S　batteries　but　filled　with　challenges.　Herein,　a　Co/CoS2　heterostructure　is　elaborately　built　to　tuning　d-orbital　electronic　structure　of　CoS2　for　a　high-performance　electrocatalyst.　Theoretical　simulations　first　evidence　that　Co　metal　as　the　electron　donator　can　form　a　built-in　electric　field　with　CoS2　and　downshift　the　d-band　center,　leading　to　the　well-optimized　adsorption　strength　for　lithium　polysulfides　on　CoS2,　thus　contributing　a　favorable　way　for　expediting　the　redox　reaction　kinetics　of　LiPSs.　As　verification　of　prediction,　a　Co/CoS2　heterostructure　implanted　in　porous　hollow　N,　S　co-doped　carbon　nanocage　(Co/CoS2@NSC)　is　designed　to　realize　the　electronic　configuration　regulation　and　promote　the　electrochemical　performance.　Consequently,　the　batteries　assembled　with　Co/CoS2@NSC　cathode　display　an　outstanding　specific　capacity　and　an　admirable　cycling　property　as　well　as　a　salient　property　of　8.25 mAh cm−2　under　8.18 mg cm−2.　The　DFT　calculation　also　reveals　the　synergistic　effect　of　N,　S　co-doping　for　enhancing　polysulfide　adsorption　as　well　as　the　detriment　of　excessive　sulfur　doping.　©　2023　Wiley-VCH　GmbH.