Delicate　design　high-efficiency　sulfur　electrocatalysts　is　crucial　for　suppressing　the　shuttle　effect　of　soluble　lithium　polysulfides　(LiPSs)　and　improving　the　electrochemical　performance　in　lithium-sulfur　(Li-S)　electrochemistry.　Herein,　a　self-supported　hierarchical　NiCo2Se4@Ni0.85Se/MoSe2　electrocatalyst　with　abundant　heterointerfaces　and　anion　vacancies　that　directly　grows　on　carbon　cloth　is　elaborately　designed　to　accelerate　the　sulfur　redox　reaction　kinetics　effectively.　Noteworthy,　the　abundant　heterointerfaces　coupling　with　anion　vacancies　greatly　facilitate　the　electron　transfer,　strengthen　the　chemical　adsorption,　provide　sufficient　active　sites,　and　enhance　the　catalytic　activity.　Additionally,　the　hierarchical　hollow　arrayed　architecture　can　guide　the　Li2S　deposition,　relieve　the　volume　expansion,　and　maintain　the　structural　stability.　Consequently,　the　Li-S　batteries　with　CC@NiCo2Se4@Ni0.85Se/MoSe2　exhibit　exceptional　electrochemical　performance　and　high　sulfur　utilization　even　under　high　sulfur　loading.　More　importantly,　the　pouch　cells　are　fabricated　to　demonstrate　the　potential　for　practical　applications.　Furthermore,　the　integration　of　experimental　and　computational　studies　confirms　that　the　Ni0.85Se/MoSe2　heterostructure　possesses　stronger　chemical　adsorption　and　reduced　energy　barrier　for　LiPSs　conversion　than　MoSe2.　Interestingly,　it　is　also　discovered　that　the　incorporation　of　Ni0.85Se　promotes　the　in　situ　lithium　ions　intercalation　in　MoSe2,　which　is　conductive　to　further　performance　enhancement.　This　study　provides　new　inspiration　for　the　hierarchical　engineering　of　electrocatalysts　toward　high-performance　Li-S　batteries.　©　2025　Wiley-VCH　GmbH.