The　commercialization　of　Li–S　batteries　is　severely　hampered　by　the　electrically　insulated　nature　of　S　and　the　discharge　product　Li2S,　the　shuttle　effect　of　lithium　polysulfides　(LiPSs),　and　the　slow　redox　kinetics　between　Li2S2/Li2S.　Herein,　a　composite　of　Co–Ni　bimetallic　selenide　nanoparticles　embedded　in　honeycomb　porous　carbon　(Co–Ni–Se@C)　is　prepared　and　used　as　a　multifunctional　interlayer　on　the　separator　to　solve　the　above-mentioned　challenges　in　Li–S　batteries.　The　Co–Ni–Se@C　composite　with　high　electrical　conductivity　can　not　only　accelerate　Li+　and　electronic　transfer　but　also　have　good　chemisorption　and　catalytic　activity　for　LiPSs,　which　can　maximize　the　utilization　of　sulfur　active　material.　As　expected,　Li–S　batteries　assembled　with　Co–Ni–Se@C-PP　separator　exhibit　excellent　electrochemical　performance,　including　high　initial　discharge　capacity　of　1245　mAh　g−1　at　0.2　C,　superior　long　cycling　stability　with　a　0.066　%　decay　per　cycle　at　1.0　C,　and　an　excellent　rate　capacity　of　674　mAh　g−1　at　5.0　C.　In　addition,　a　satisfactory　capacity　of　1174　mAh　g−1　is　achieved　with　a　high　sulfur　loading　of　3.7　mAh　g−1　and　a　low　E/S　ratio　of　10　μL　mg−1.　This　work　provides　a　new　insight　into　the　application　of　bimetallic　selenides　in　high-performance　Li–S　batteries.　©　2024　Elsevier　B.V.