The　practical　applications　of　lithium-sulfur　(Li-S)　batteries　are　severely　impeded　by　the　shuttle　effect　of　soluble　lithium　polysulfides　(LiPSs),　sluggish　redox　reaction　kinetics,　and　insulating　nature　of　sulfur　and　its　discharge　products　(Li2S2/Li2S).　Developing　sulfur　electrocatalysts　with　high　electrocatalytic　activity　to　accelerate　the　redox　kinetics　and　polysulfide　trapping　is　critical　for　Li-S　batteries　but　remains　a　grand　challenge.　In　this　contribution,　we　demonstrate　the　delicate　design　and　synthesis　of　oxygen-incorporated　heterophase　cobalt　vanadium　selenide　nanoplates　with　dense　crystalline/amorphous　interfacial　sites　(denoted　as　DC/A　O-CoVSe　NPs)　as　high-efficiency　sulfur　electrocatalysts　for　Li-S　batteries.　Such　DC/A　O-CoVSe　NPs　possess　high　electronic　conductivity　and　electrocatalytic　activity.　Besides,　the　abundant　exposed　crystalline/amorphous　interfacial　sites　serve　as　efficient　adsorption-catalytic　centers　to　accelerate　the　conversion　kinetics　and　alleviate　the　shuttle　effect.　Moreover,　incorporation　of　oxygen　further　increases　their　affinity　to　LiPSs　because　of　the　introduction　of　more　Li-O　interactions.　Benefiting　from　the　multifarious　advantages,　Li-S　batteries　with　DC/A　O-CoVSe　NP　modified　separators　exhibit　high　discharge　capacity　(1400.1　mA　h　g−1　at　0.1C),　excellent　rate　capability　(683.8　mA　h　g−1　at　5C),　and　good　long-term　durability　(672.4　mA　h　g−1　at　1C　after　500　cycles　with　a　low　decay　rate　of　0.066%　per　cycle).　Even　at　a　high　sulfur　loading　of　5.6　mg　cm−2,　the　battery　still　delivers　a　decent　reversible　capacity　of　658.8　mA　h　g−1　at　0.2C　after　100　cycles,　indicating　its　great　potential　for　practical　applications.　This　work　could　provide　a　rational　viewpoint　for　developing　high-efficiency　sulfur　electrocatalysts　towards　future　advanced　Li-S　energy　storage　systems.　©　2024　The　Royal　Society　of　Chemistry.