Core–shell Cu@Cu6Sn5 nanowires with three-dimensional structure have been successfully synthesized via an electrodeposition process, using Cu(OH)2 nanorods prepared by anodization as the substrate. Different temperatures have been employed to heat-treat Sn–Cu composites. After heat-treated at 80°C, strong adherence of the active material Cu6Sn5 to the current collector is achieved, and the crystal structure becomes more stable, thus delivering best cycling performance of 0.162mAhcm−2 after 200 cycles at 1C. Furthermore, superior rate capability (as high as 20C) is also obtained.