In-situ　epitaxial　graphene　(EG)　strategy　is　adopted　to　activate　the　electrochemically　inactive　silicon　carbide　(SiC)　by　constructing　Schottky　junction　for　high-performance　anode　of　lithium-ion　battery　(LIB).　Raman　and　Hall　measurements　confirm　the　high　quality　and　electronic　mobility　of　EG.　Refined　structural　characterization　(XPS　and　XANES)　and　theoretical　analysis　indicate　that　the　interfacial　coupled　structure　exhibits　Schottky　junction　with　an　inherent　built-in　electric　field,　and　the　strong　interfacial　Si–C　interaction　could　reinforce　the　interfacial　coupling.　This　prototype　can　systematically　comprehend　interfacial　electronic　properties　and　transport　mechanisms.　As　a　proof-of-concept　study,　this　interfacially　designed　Schottky　junction　is　demonstrated　to　promote　both　the　surface　electron　densities　and　charge　carriers　transportation　efficiency　for　LIB　anodes.　Even　at　10.0　A　g−1,　the　EG@SiC　anode　can　still　deliver　a　capacity　of　322.1　mA　h　g−1.　The　ex-situ　XRD,　HRTEM,　and　XPS　analysis　confirm　the　reversible　intercalation　reaction　mechanism　and　excellent　structural　stability.　The　proposed　strategy　of　constructing　Schottky　junction　through　interlayer　engineering　can　construct　advanced　SiC-based　electrodes　for　high-performance　rechargeable　batteries.　©　2020　Elsevier　Ltd