Macroporous material of Sn–Cu alloy of different pore sizes designated as anode in lithium-ion batteries were fabricated through colloidal crystal template method. The structure and electrochemical properties of the macroporous Sn–Cu alloy electrodes were examined by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and galvanostatic cycling. The results demonstrated that the electrodes of macroporous Sn–Cu alloy with pore size respectively of 180 and 500nm can deliver reversible capacity of 350 and 270mAhg−1 up to 70th cycles of charge/discharge. The cycle performance of the macroporous Sn–Cu alloy of 180nm in pore size is better than that of the macroporous Sn–Cu alloy with 500-nm-diameter pores. It has revealed that the porous structure of the macroporous Sn–Cu alloy material is of importance to strengthen mechanically the electrode and to reduce significantly the effect of volume expansion during cycling.