A silicon hierarchical structure composed of 20 nm Si nanoparticles (Si-20) is synthesized using a solvothermal method. After coating with a carbon layer by pyrolysis of acetylene gas, the fabricated Si-20@C composites exhibit a superior cycling performance with 915.8 mA h g(-1) at 3.6 A g(-1) over 500 cycles and a high rate performance with 746.2 mA h g(-1) at 10.8 A g(-1).