In situ growth of hierarchical scale-like CuCl on homologous Cu foam substrate for lithium ion battery (LIB) was achieved via facile anodization of Cu and the following rapid deposition of insoluble CuCl. The obtained hierarchical scale-like CuCl/Cu foam electrode were investigated in terms of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), galvanostatic charge/discharge, rate performance, cycle stability and AC impedance. When used as the anode in LIB, the as-synthesized electrode with multi-scaled pores delivered satisfactory electrochemical performances. Particularly, the reversible discharge capacity was still maintained at about 197.2mAh/g even after 1000 cycles at high rate of 10C, indicating excellent endurance and structural stability during the fast cyclic charge/discharge. It can be concluded that the developed hierarchical scale-like CuCl/Cu foam electrode can not only improve the electronic conductivity, but also buffer the structure strain during long term cyclic lithiation/delithiation and maintain the structural stability. Seemingly, hierarchical CuCl with high Li-storage activity and highly conductive three dimensional (3D) porous homologous Cu foam substrate jointly contributed to high electrochemical performances.