The　sluggish　kinetics　of　multiphase　sulfur　conversion　with　homogeneous　and　heterogeneous　electrochemical　processes,　causing　the　“shuttle　effect”　of　soluble　polysulfide　species　(PSs),　is　the　challenges　in　terms　of　lithium–sulfur　batteries　(LSBs).　In　this　paper,　a　Mn3O4−x　catalyst,　which　has　much　higher　activity　for　heterogeneous　reactions　than　for　homogeneous　reactions　(namely,　preferential-activity　catalysts),　is　designed　by　surface　engineering　with　rational　oxygen　vacancies.　Due　to　the　rational　design　of　the　electronic　structure,　the　Mn3O4−x　catalyst　prefers　to　accelerate the　conversion　of　Li2S4　into　Li2S2/Li2S　and　optimize　Li2S　deposition,　reducing　the　accumulation　of　PSs　and　thus　suppressing　the　“shuttle　effect.” Both　density　functional　theory　calculations　and　in　situ　X-ray　diffraction　measurements　are　used　to　probe　the　catalytic　mechanism　and　identify　the　reaction　intermediates　of　MnS　and　LiyMnzO4−x　for　fundamental　understanding.　The　cell　with　Mn3O4−x　delivers　an　ultralow　attenuation　rate　of　0.028%　per　cycle　over　2000　cycles　at　2.5　C.　Even　with　sulfur　loadings　of　4.93　and　7.10　mg　cm−2　in　a　lean　electrolyte　(8.4　µL　mg　s−1),　the　cell　still　shows　an　initial　areal　capacity　of　7.3　mAh　cm−2.　This　study　may　provide　a　new　way　to　develop　preferential-activity　heterogeneous-reaction　catalysts　to　suppress　the　“shuttle　effect”　of　the　soluble　PSs　generated　during　the　redox　process　of　LSBs.　©　2022　The　Authors.　Carbon　Energy　published　by　Wenzhou　University　and　John　Wiley　&　Sons　Australia,　Ltd.