Silicon is a promising alternative anode material since it has a ten times higher theoretical specific capacity than that of a traditional graphite anode. However, the poor cycling stability due to the huge volume change of Si during charge/discharge processes has seriously hampered its widespread application. To address this challenge, we design a silicon hollow sphere nanostructure by selective etching and a subsequent magnesiothermic reduction. The Si hollow spheres exhibit enhanced electrochemical properties compared to the commercial Si nanoparticles. The initial discharge and charge capacities of the Si hollow sphere anode are 2215.8 mAh g-1 and 1615.1 mAh g-1 with a high initial coulombic efficiency (72%) at a current density of 200 mA g-1, respectively. In particular, the reversible capacity is 1534.5 mAh g-1 with a remarkable 88% capacity retention against the second cycle after 100 cycles, over four times the theoretical capacity of the traditional graphite electrode. Therefore, our work demonstrates the considerable potential of silicon structures for displacing commercial graphite, and might open up new opportunities to rationally design various nanostructured materials for lithium ion batteries.