Wide　operation　temperature　is　the　crucial　objective　for　an　energy　storage　system　that　can　be　applied　under　harsh　environmental　conditions.　For　lithium‐sulfur　batteries,　the　“shuttle　effect”　of　polysulfide　intermediates　will　aggravate　with　the　temperature　increasing,　while　the　reaction　kinetics　decreases　sharply　as　the　temperature　decreasing.　In　particular,　sulfur　reaction　mechanism　at　low　temperatures　seems　to　be　quite　different　from　that　at　room　temperature.　Here,　through　in　situ　Raman　and　electrochemical　impedance　spectroscopy　studies,　the　newly　emerged　platform　at　cryogenic　temperature　corresponds　to　the　reduction　process　of　Li2S8　to　Li2S4,　which　will　be　another　rate‐determining　step　of　sulfur　conversion　reaction,　in　addition　to　the　solid‐phase　conversion　process　of　Li2S4　to　Li2S2/Li2S　at　low　temperatures.　Porous　bismuth　vanadate　(BiVO4)　spheres　are　designed　as　sulfur　host　material,　which　achieve　the　rapid　snap‐transfer‐catalytic　process　by　shortening　lithium‐ion　transport　pathway　and　accelerating　the　targeted　rate‐determining　steps.　Such　promoting　effect　greatly　inhibits　severe　“shuttle　effect”　at　high　temperatures　and　simultaneously　improves　sulfur　conversion　efficiency　in　the　cryogenic　environment.　The　cell　with　the　porous　BiVO4　spheres　as　the　host　exhibits　excellent　rate　capability　and　cycle　performance　under　wide　working　temperatures.