The　intrinsically　sluggish　sulfur　reduction　reaction　kinetics　and　serious　shuttle　effect　of　soluble　lithium　polysulfides　(LiPSs)　severely　impede　the　practical　commercialization　of　lithium-sulfur　(Li-S)　batteries.　Herein,　self-supported　tungsten　nitride　and　carbide　heterostructures　with　vanadium　doping　that　are　directly　grown　on　carbon　cloth　substrate　(CC@V-W2N/WC1-x)　are　creatively　designed　for　Li-S　batteries,　which　can　tandemly　catalyze　the　liquid–liquid　conversion　and　liquid–solid　conversion　of　polysulfide　intermediate　free　of　any　interference　from　polymer　binders　and　conductive　additives.　Noteworthy,　the　rich　heterointerfaces　and　vanadium　doping　are　beneficial　for　rapid　charge　transfer,　strong　chemical　adsorption　toward　LiPSs,　massive　exposed　catalytically　active　sites,　and　remarkable　catalytic　activities.　Consequently,　Li-S　batteries　assembled　with　the　CC@V-W2N/WC1-x/S　cathodes　exhibit　high　sulfur　utilization,　superior　rate　capability,　and　decent　long-term　cycling　stability.　Furthermore,　experimental　analyses　and　theoretical　calculations　jointly　substantiate　that　the　V-W2N　component　is　more　effective　in　catalyzing　the　conversion　of　long-chain　LiPSs,　while　the　V-WC1-x　benefits　the　favorable　Li2S　deposition　kinetics.　More　importantly,　the　Li-S　pouch　cells　are　also　fabricated　to　demonstrate　their　feasibility　for　practical　applications.　This　work　not　only　highlights　the　significance　of　tandem　catalysis　on　the　consecutive　conversion　of　LiPSs　but　also　provides　a　feasible　avenue　for　developing　highly　efficient　electrocatalysts　toward　high-performance　Li-S　batteries.　©　2024　Wiley-VCH　GmbH.