The　use　of　p-block　metals　to　accelerate　the　sulfur　reduction　reaction　(SRR)　in　lithium-sulfur　(Li-S)　batteries　is　emerging.　However,　the　d‐electrons　inertia　of　p-block　metal　endows　the　weak　adsorption　and　catalytic　ability　for　SRR,　limiting　catalyst　design.　Herein,　we　fabricate　an　asymmetrically　coordinated　p-block　indium　trisulfide　by　coordination　engineering　with　P　doping　and　sulfur　vacancies　(P-In2S3-x)　for　SRR.　The　unique　coordination　engineering　induces　the　rearrangement　of　electrons　in　the　s/p/d　hybrid　orbital,　causing　that　P-In2S3-x　shifts　electron　states　from　low　to　high　spin,　generating　more　unpaired　electrons.　The　obtained　high-spin　configuration　achieves　that　electron　transition　to　a　higher　energy　level　to　activate　d‐electrons　of　p-block　metals,　which　enables　a　novel　d-p　coupling　between　d　orbitals　of　In　atoms　and　the　p　orbitals　of　S　atoms　in　LiPSs,　improving　adsorption　and　catalytic　ability　of　p-block　metals　for　SRR.　Consequently,　cell　with　P-In2S3-x　achieves　excellent　capacity　retention,　with　a　very　low　decay　rate　(0.036　%　per　cycle　at　5　C　over　1000　cycles)　and　high　performance　at　0°C　(760　mAh　g−1　at　1　C).　This　study　offers　a　strategy　for　modulation　d‐electrons　activity　p-block　metals　by　tailoring　electron　spin　to　boost　catalytic　efficiency　in　Li-S　batteries.　©　2025