In this work, we have developed a simple approach to rationally design and controllably synthesize custard-apple-like Si@N, O-dual-doped carbon with hierarchical porosity. This material delivers outstanding reversible capacity at high current density with good rate capability and a long cycling life of over 4000 cycles as an anode for Li-ion batteries. A detailed eletrochemical kinetic analysis reveals that the lithium ion charge storage partly depends on the capacitance-controlled behavior, with a high capacitive contribution up to 30.3% for the total capacity at 1mVs−1. The impressive eletrochemical performance demonstrates that the Si@mNOC anode has great potential to meet the challenges arising from the use of Si nanoparticles as anode for next-generation large-scale energy storage.