Silicon has a high theoretical capacity, still limits its application on Si-based anodes due to the problems of low electric conductivity, large volume change, continuous formation of unstable solid electrolyte interphase layer, and easy fracture during lithiation and delithiation process. Despite various carbon coating approaches are developed to fabricate carbon coated silicon core-shell and yolk-shell nanocomposites with improved electrochemical performance, the challenges including poor long-term cyclability, low Si mass ratio, and scalability remains. To overcome these challenges, we design an interfacial microporous carbon coating strategy on silicon nanoparticles to form homogeneous coaxial core-shell nanostructures. This synthesis sol-gel approach is simple, easy to scale up, and direct growth phenolic resins on the surface with uniform and controllable thickness. Additionally, the fabricated carbon layers form the microporous structures and phenolic resin frameworks, thus enabling the fast lithium ion transport and formation of stable solid electrolyte interphase film. By finely controlling the thickness of this phenolic resin-based carbon of 10 nm, excellent protection of silicon nanoparticles as well as high electrochemical performance are achieved, delivering a high capacity of 1006 mA h g−1 and Coulombic efficiency of >99.5% after 500 times at a current density of 500 mA g−1.