The　intrinsic　clustering　behavior　and　kinetically　sluggish　conversion　process　of　lithium　polysulfides　seriously　limit　the　electrochemical　reversibility　of　sulfur　redox　reactions　in　lithium-sulfur　(Li-S)　batteries.　Here,　we　introduce　molybdenum　pentachloride　(MoCl5)　into　the　electrolyte　which　could　coordinate　with　lithium　polysulfides　and　inhibit　their　intrinsic　clustering　behavior,　subsequently　serving　as　an　improved　mediator　with　the　bi-functional　catalytic　effect　for　Li2S　deposition　and　activation.　Moreover,　the　coordination　bonding　and　accelerated　conversion　reaction　can　also　greatly　suppress　the　dissolution　and　shuttling　of　polysulfides.　Consequently,　such　polysulfide　complexes　enable　the　Li-S　coin　cell　to　exhibit　good　long-term　cycling　stability　with　a　capacity　decay　of　0.078　%　per　cycle　after　400　cycles　at　2　C,　and　excellent　rate　performance　with　a　discharge　capacity　of　589　mAh/g　at　4　C.　An　area　capacity　of　3.94　mAh/cm2　is　also　achieved　with　a　high　sulfur　loading　of　4.5　mg/cm2　at　0.2　C.　Even　at　-20　°C,　the　modified　cell　maintains　standard　discharge　plateaus　with　low　overpotential,　delivering　a　high　capacity　of　741　mAh/g　at　0.2　C　after　80　cycles.　The　low-cost　and　convenient　MoCl5　additive　opens　a　new　avenue　for　the　effective　regulation　of　polysulfides　and　significant　enhancement　in　sulfur　redox　conversion.　©　2025