A novel C/SiO₂ composite with a carbon–silica–carbon (C-mcms) three layer structure was synthesized and evaluated as an anode material for high-energy lithium ion batteries. The C-mcms exhibits an excellent capacity of about 1055 mA h g⁻¹ at a current density of 500 mA g⁻¹ after 150 cycles without detectable decay, and high-rate capability, which is superior to other similar composites without the carbon core or the carbon shell. The results indicate the structural effect on the enhancement of the electrochemical properties: the SiO₂ nanoparticles are completely confined between the carbon shell and the carbon core; the two carbon parts work together to keep the structural integrity and to keep the electrode highly conductive and active during cycling, which guarantees high capacity and cycle stability; the interior pores and voids among the SiO₂ nanoparticles can provide free space to accommodate the volume change and buffer the volume effect of the electrode during lithiation/delithiation.