A Si-based alloy as the anode material in Li-ion batteries has advantages of safety and excellent performances, but poor electronic conductivity and excessive volume expansion limit the long cycle life required for practical application. In this work, in order to solve these problems, a core-shell nanocomposite has been developed, which is composed of a Si core and NiSi2/Ni shell with a carbon layer coating as the outer surface, which is referred to as a Si@NiSi2/Ni/C nanocomposite. Results show a reversible charge capacity of 1194mAhg−1 and 98% retention after 105 cycles, which are superior to its Si/C and NiSi2/Si counterparts. Furthermore, the fabrication method used has advantages of low cost and easy operation, which make it feasible to commercialize the Si@NiSi2/Ni/C nanocomposite as the anode in a lithium-ion battery.