Designing　heterostructured　hosts　is　one　of　the　promising　strategies　to　mitigate　the　shuttle　effect　of　dissolved　lithium　polysulfides　(LiPSs)　and　accelerate　the　redox　reaction　kinetics　between　LiPSs　and　Li2S,　which　could　boost　the　electrochemical　performance　of　lithium-sulfur　batteries　(LSBs).　Among　such　hosts,　polar　TiO2　and　conductive　porous　carbon　are　an　optimal　and　common　combination.　However,　there　exist　few　investigations　to　systematically　evaluate　the　effect　of　the　TiO2　phase　structure　(i.e.,　anatase　and　rutile)　of　the　TiO2/C　heterointerfaces　on　the　catalytic　efficiency　toward　the　LiPS　conversion.　Herein,　ultrafine　anatase　and　rutile　TiO(2　)nanoparticle　(3-5　nm)　modified　macroporous　carbon　microspheres　(AT@MC　and　RT@MC)　were　synthesized　as　the　sulfur　hosts,　respectively.　The　smaller　the　size　of　the　TiO2　nanoparticles,　the　greater　the　TiO2/C　heterointerfaces.　And　both　experimental　tests　and　theoretical　calculations　implied　that,　compared　with　rutile　TiO2,　the　TiO2/C　heterointerfaces　constructed　by　anatase　TiO2　demonstrated　a　higher　catalytic　efficiency　due　to　the　stronger　absorbability　toward　LiPSs　and　the　lower　energy　barriers　during　the　electrochemical　process.　As　a　result,　the　S@AT@MC　electrodes　delivered　a　high　specific　capacity　and　a　capacity　decay　rate　of　0.056%　per　cycle　for　500　cycles.　This　work　furnishes　guidance　on　the　design　of　TiO2-based　heterostructured　hosts　for　high-performance　LSBs.