Thin film Sn–Cu anodes with high Cu content were prepared by electron-beam evaporation deposition using Cu substrate as current collector. Annealing, with the condition being determined by DSC, was used to improve the performance of these electrodes. X-ray diffraction (XRD), scanning probe microscopy (SPM), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were used to characterize the structure and composition of the Sn–Cu thin film electrodes. Cyclic voltammetry and galvanostatical charge–discharge measurement were carried out to characterize the electrochemical properties of the as-deposited and annealed electrodes. ɛ-Cu3Sn intermetallic phase was formed and interface strength between deposited active materials layer and current collector was enhanced by annealing the as-deposited film under suitable condition. The annealed thin film electrode showed good cycleability and had no phase change during cycling. Although large initial capacity loss was found associated with SEI formation due to increase of surface roughness of annealed electrode, a stable discharge capacity near 300mAh/g with Coulomb efficiency of about 96% was obtained at voltage window of 0.1–2.0V and a discharge capacity of about 200mAh/g and Coulomb efficiency of 97% were kept stable up to 30th cycle at a narrower voltage window of 0.2–1.5V versus Li/Li+.