Cu6Sn5 alloys were successfully electrodeposited on rough Cu foils and smooth Cu sheets using a facile one-step electrodepositing method, and their structural and electrochemical properties were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), galvanostatic charging/discharging testing and electrochemical impedance spectroscopy (EIS). The influence of surface morphology of the current collectors on the cycleability and the interfacial performance of the Cu6Sn5 alloy electrode are both discussed. The results demonstrate that the Cu6Sn5 alloy electrode on the rough Cu foil presented better electrochemical performance than that on the smooth Cu sheet because its rough surface could buffer the volume changes to some extent. The first discharging (lithiation) and charging (delithiation) capacities were measured at 462 and 405 mAh g(-1) respectively with high initial coulomb efficiency of 88%, with charging capacity in the 50th cycle remaining 76% of that in the first cycle. The phase transformation during initial lithiation was detected by electrochemical impedance spectroscopy (EIS) and its trend versus electrode potential is also discussed.