Micro-scaled spherical CoSn2/Sn alloy powders synthesized from oxides of Sn and Co via carbothermal reduction at 800°C were examined for use as anode materials in Li-ion battery. The phase composition and particle morphology of the CoSn2/Sn alloy composite powders were investigated by XRD, SEM and TEM. The prepared CoSn2/Sn alloy composite electrode exhibits a low initial irreversible capacity of ca. 140mAhg−1, a high specific capacity of ca. 600mAhg−1 at constant current density of 50mAg−1, and a good rate capability. The stable discharge capacities of 500–515mAhg−1 and the columbic efficiencies of 95.8–98.1% were obtained at current density of 500mAg−1. The relatively large particle size of CoSn2/Sn alloy composite powder is apparently favorable for the lowering of initial capacity loss of electrode, while the loose particle structural characteristic and the Co addition in Sn matrix should be responsible for the improvement of cycling stability of CoSn2/Sn electrode.