Engineering　heterogeneous　composite　electrodes　consisting　of　multiple　active　components　for　meeting　various　electrochemical　and　structural　demands　have　proven　indispensable　for　significantly　boosting　the　performance　of　lithium-ion　batteries　(LIBs).　Here,　a　novel　design　of　ZnS/Sn　heterostructures　with　rich　phase　boundaries　concurrently　encapsulated　into　hierarchical　interconnected　porous　nitrogen-doped　carbon　frameworks　(ZnS/Sn@NPC)　working　as　superior　anode　for　LIBs,　is　showcased.　These　ZnS/Sn@NPC　heterostructures　with　abundant　heterointerfaces,　a　unique　interconnected　porous　architecture,　as　well　as　a　highly　conductive　N-doped　C　matrix　can　provide　plentiful　Li+-storage　active　sites,　facilitate　charge　transfer,　and　reinforce　the　structural　stability.　Accordingly,　the　as-fabricated　ZnS/Sn@NPC　anode　for　LIBs　has　achieved　a　high　reversible　capacity　(769　mAh　g(-1),　150　cycles　at　0.1　A　g(-1)),　high-rate　capability　and　long　cycling　stability　(600　cycles,　645.3　mAh　g(-1)　at　1　A　g(-1),　92.3%　capacity　retention).　By　integrating　in　situ/ex　situ　microscopic　and　spectroscopic　characterizations　with　theoretical　simulations,　a　multiscale　and　in-depth　fundamental　understanding　of　underlying　reaction　mechanisms　and　origins　of　enhanced　performance　of　ZnS/Sn@NPC　is　explicitly　elucidated.　Furthermore,　a　full　cell　assembled　with　prelithiated　ZnS/Sn@NPC　anode　and　LiFePO4　cathode　displays　superior　rate　and　cycling　performance.　This　work　highlights　the　significance　of　chemical　heterointerface　engineering　in　rationally　designing　high-performance　electrodes　for　LIBs.