With a high specific capacity (4200 mA h g⁻¹), silicon based materials have become the most promising anode materials in lithium-ions batteries. However, the large volume expansion makes the capacity reduce rapidly. In this work, a periodic silicon/carbon (Si/C) multilayer thin film was synthesized by magnetron sputtering method on copper foil. The titanium (Ti) film (about 20 nm) as the transition layer was deposited on the copper foil prior to the deposition of the multilayer film. Superior electrochemical lithium storage performance was obtained by the multilayer thin film. The initial discharge and charge specific capacity of the Si (15 nm)/C (5 nm) multilayer film anode are 2640 mA h g⁻¹ and 2560 mA h g⁻¹ with an initial coulombic efficiency of ∼97%. The retention specific capacity is about 2300 mA h g⁻¹ and there is ∼87% capacity retention after 200 cycles.