A three-dimensional Sn electrode is fabricated by the electrodeposition of Sn on a porous Cu foam substrate that consists of grape-like Cu nanodeposits. It is revealed from the XRD results that a small amount of Cu6Sn5 is formed at the interface of Sn deposits and the Cu foam, thereby forming Sn–Cu6Sn5/Cu foam electrode. The electrode shows better cyclic performance and higher charge capacity than the Sn electrode electrodeposited on a smooth Cu foil does. The improved electrochemical performances of the Sn–Cu6Sn5/Cu foam electrode is due to the fact that the porous Cu foam accommodates the volumetric expansion of Sn–Cu6Sn5, and hence inhibits the pulverization or delamination of the active materials from the substrate. Furthermore, ex situ XRD analysis and SEM observation demonstrate that Sn deposits electrodeposited on the Cu foam are gradually blended with the Cu deposits, causing the transformation of Sn into Cu6Sn5. The phase transformation of Sn into Cu6Sn5 enhances the bonding force between the Sn and the Cu foam, and reducing the volume changes of active materials during cycling.