Thin film Si/Ag and (Si–Zr)/Ag multilayer electrodes are fabricated on a Cu substrate by alternate sputtering from Si (–Zr) and Ag at room temperature, and their electrochemical properties are investigated. The insertion of the Ag layer into the Si layer improves the cycling performance. The cyclability can be further improved by doping Zr into the Si layer of the Si/Ag multilayer thin films. The effects of the electrode configuration and the contact stability between the current-collecting layer and the electrode on the cycling performance are discussed.