Silicon-based nanostructures are receiving intense interest in lithium-ion batteries (LIBs) because they have ultrahigh lithium ion storage ability. However, the fast capacity fading induced by the considerably tremendous volume changes of Si anode during the Li-ion intercalation processes as well as the low intrinsic electric conductivity have hindered its deployment. Herein, we initially developed an effective technique to synthesize the core-shell Si/nitrogen-doped carbon (Si/N[Formula: see text]C), composite by combining in situ interfacial polymerization and decorate with melamine, followed by carbonization. When used as anode material for LIBs, the Si/N[Formula: see text]C composite delivered a notable reversible capacity (1084 mAh g[Formula: see text] at 0.2 A g[Formula: see text] for 50 cycles) and high rate capability (495 mAh g[Formula: see text] at 1 A g[Formula: see text]).