Three-dimensional porous Cu/Cu2O, CuO, CuO/NiO were prepared on Ni foam by a simple two step method which consist of a replacement reaction and subsequent thermal treatment method at various temperature. The morphology and microstructure of the samples were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical properties of the samples were evaluated by galvanostatic discharge–charge cycling, cyclic voltammetry and impedance spectral measurements on cells with lithium discs as counter electrode and reference electrode. Compared to Cu/Cu2O and CuO/NiO, the sample of CuO obtained at 400°C exhibited the best electrochemical performance which delivered a reversible capacity of 605.3mAhg−1 (89.8% of the theoretical capacity) after 50 cycles at the current density of 100mAg−1, without noticeable capacity fading. The excellent electrochemical performance of porous CuO can be attributed to the three-dimensional porous structure, which cannot only provide large surface area but also facilitate Li+ and electron transfer, and the strong connection between active materials and Ni foam can promote better intrinsic kinetics.