Hollow core-shell structured Si/C nanocomposites were prepared to adapt for the large volume change during a charge-discharge process. The Si nanoparticles were coated with a SiO2 layer and then a carbon layer, followed by etching the interface SiO2 layer with HF to obtain hollow core-shell structured Si/C nanocomposites. The Si nanoparticles are well encapsulated in a carbon matrix with an internal void space between the Si core and the carbon shell. The hollow core-shell structured Si/C nanocomposites demonstrate a high specific capacity and excellent cycling stability, with capacity decay as small as 0.02% per cycle. The enhanced electrochemical performance can be attributed to the fact that the internal void space can accommodate the volume expansion of Si during lithiation, thus preserving the structural integrity of electrode materials, and the carbon shell can increase the electronic conductivity of the electrode.