As a promising anode material for lithium ion battery, nano-Cu coated porous Si powder was fabricated through two stages: first, preparation of porous nano Si fibers by acid-etching Al-Si alloy powder; second, modified by nano-Cu particles using an electroless plating method. The nano-Cu particles on the surface of nano-Si fibers, not only increase the conductivity of material, but also inhibit the fuse process between nano Si fibers during charge/discharge cycling process, resulting in increased cycling stability of the material. In 1M LiPF6/EC: DMC (1:1)+1.5wt% VC solution at current density of 200mAg−1, the 150th discharge capacity of nano-Cu coated porous Si electrode was 1651mAhg−1 with coulombic efficiency of 99%. As anode material for lithium ion battery, nano-Cu coated porous Si nano fiber material is easier to prepare, costs less, and produces higher performance, representing a promising approach for high energy lithium ion battery application.