Silicon batteries have attracted much attention in recent years due to their high theoretical capacity, although a rapid capacity fade is normally observed, attributed mainly to volume expansion during lithiation. Here, we report for the first time successful synthesis of Si/void/SiO 2 /void/C nanostructures. The synthesis strategy only involves selective etching of SiO 2 in Si/SiO 2 /C structures with hydrofluoric acid solution. Compared with reported results, such novel structures include a hard SiO 2 -coated layer, a conductive carbon-coated layer, and two internal void spaces. In the structures, the carbon can enhance conductivity, the SiO 2 layer has mechanically strong qualities, and the two internal void spaces can confine and accommodate volume expansion of silicon during lithiation. Therefore, these specially designed dual yolk-shell structures exhibit a stable and high capacity of 956mA hg -1 after 430 cycles with capacity retention of 83%, while the capacity of Si/C core-shell structures rapidly decreases in the first ten cycles under the same experimental conditions. The novel dual yolk-shell structures developed for Si can also be extended to other battery materials that undergo large volume changes.