The　practical　application　of　SnO2　anodes　in　lithium-ion　batteries　is　fundamentally　constrained　by　cascading　challenges　of　structural　degradation　and　kinetic　limitations.　We　demonstrate　a　dual-interface　engineering　strategy　through　precisely　controlled　gas-phase　phosphorization,　constructing　SnO2/Sn4P3　heterojunctions　tightly　encapsulated　within　hierarchical　carbon　frameworks　(SnO2/Sn4P3@C,　SOPC).　The　SnO2/Sn4P3　heterojunction　generates　a　built-in　electric　field,　reducing　charge　transfer　resistance　and　activation　energy　(UPS　work　function:　2.91　eV)　and　guides　LiF-rich　SEI　formation,　while　the　dual-carbon　confinement　buffers　mechanical　strain　and　ensures　the　structural　stability　with　long-term　cycling　at　high　current　density.　These　features　enable　hybrid　storage　kinetics　with　capacitive　dominance　at　high　rates　and　stable　faradaic　reactions　at　low　currents.　The　SOPC　anode　achieves　exceptional　cyclability　with　capacities　of　954.8　mA　h　g−1　after　600　cycles　at　1　A　g−1　and　118.9　mA　h　g−1　after　3000　cycles　at　20　A　g−1.　Full　cells　paired　with　LiFePO4　demonstrate　practical　viability.　This　work　establishes　a　universal　interfacial　engineering　strategy　for　high-performance　alloying/conversion　anodes,　bridging　atomic-scale　electronic　modulation　to　scalable　battery　systems.　©　2025　The　Royal　Society　of　Chemistry.