We demonstrate a simple route for preparing Si/SiO(x) urchin-like structures in which Si/SiO(x) core-shell nanocoils protruded out from the surface of bulk Si, via high-temperature annealing of Pt-decorated Si powders. The carbon-coated urchin-like anodes with micro- and nanostructured composite exhibit a significantly improved electrochemical performance with a high specific capacity of 1600 mAh/g and a superior cycling performance of 70 cycles at a rate of 0.2 C due to the nanocoil conformation and SiO(x) buffer layer. More importantly, the composite results in a significantly enhanced the volumetric capacity with ∼3780 mAh/cc, compared to bulk Si (∼2720 mAh/cc) after fully lithiation to 0 V.