Heterostructure　engineering　is　considered　a　crucial　strategy　to　modulate　the　intrinsic　charge　transfer　behavior　of　materials,　enhance　catalytic　activity,　and　optimize　sulfur　electrochemical　processes.　However,　parsing　the　role　of　heterogeneous　interface-structure　-　property　relationships　in　heterostructures　is　still　a　key　scientific　issue　to　realize　the　efficient　catalytic　conversion　of　polysulfides.　Based　on　this,　molybdenum　carbide　(Mo　2　C)　was　successfully　partial　reduced　to　molybdenum　metal　(Mo)　via　a　thermal　reduction　at　high-temperature　and　the　typical　Mo-Mo　2　C-based　Mott-Schottky　heterostructures　were　simultaneously　constructed,　which　realized　the　modulation　of　the　electronic　structure　of　Mo　2　C　and　optimized　the　conversion　process　of　lithium　polysulfides　(LPS).　Compared　with　single　molybdenum　carbide,　the　modulated　molybdenum　carbide　acts　as　an　electron　donor　with　stronger　Mo　-S　bonding　strength　as　well　as　higher　polysulfide　adsorption　energy,　faster　Li　2　S　conversion　kinetics,　and　greatly　facilitates　the　adsorption　-＞　catalysis　process　of　LPS.　As　a　result,　yolk-shell　Mo-Mo　2　C　heterostructure　(C@Mo-Mo　2　C)　exhibits　excellent　cycling　performance　as　a　sulfur　host,　with　a　discharge　specific　capacity　of　488.41　mAh　g　-1　for　C@Mo-Mo　2　C/S　at　4　C　and　present　an　excellent　high　-rate　cyclic　performance　accompanied　by　capacity　decay　rate　of　0.08　%　per　cycle　after　400　cycles　at　2　C.　Heterostructure-acting　Mo　2　C　electron　distribution　modulation　engineering　may　contributes　to　the　understanding　of　the　structure　-interface　-property　interaction　law　in　heterostructures　and　further　enables　the　efficient　modulation　of　the　chemical　behavior　of　sulfur.