The　sluggish　reaction　kinetics　and　formidable　shuttle　effect　of　soluble　lithium　polysulfides　(LiPSs)　are　thorny　problems　for　the　future　industrialization　of　lithium-sulfur　(Li-S)　batteries.　Therefore,　exploring　efficient　electrocatalysts　to　capture　LiPSs　and　accelerate　their　conversion　is　highly　desirable　yet　tremendously　challenging.　Herein,　a　high-efficiency　Bi/Bi2O3/VMoN@rGO　electrocatalyst　with　multifunctional　active　sites　and　multilevel　heterointerfaces　is　elaborately　designed　for　Li-S　batteries.　Noteworthy,　the　multilevel　heterointerfaces　can　greatly　modulate　the　electron　distribution,　facilitate　the　charge　transfer,　optimize　the　chemical　absorption,　and　enhance　the　intrinsic　activity,　while　rGO　contributes　to　high　electrical　conductivity,　sufficient　active　sites,　and　robust　structural　stability.　Thanks　to　the　synergy　of　different　components,　Li-S　batteries　employing　the　Bi/Bi2O3/VMoN@rGO　functional　separators　exhibit　impressive　electrochemical　performance　and　high　sulfur　utilization　even　under　high　sulfur　loading.　More　importantly,　it　is　discovered　that　Bi　and　Bi2O3　experience　an　electrochemical　phase　evolution　to　generate　Bi2S3　with　amorphous　and　crystalline　phases,　thereby　bringing　in　unexpected　performance　enhancement.　Furthermore,　experimental　results　and　theoretical　calculations　authenticate　that　a　reduced　Li2S　decomposition　energy　barrier　is　achieved　after　the　in　situ　electrochemical　reconstruction.　This　work　not　only　provides　new　mechanistic　insights　into　developing　high-efficiency　sulfur　electrocatalysts　but　also　sheds　light　on　regulating　the　catalytic　activity　via　self-reconstruction.