Sputtering growth of a Sn/Li2O multilayer composite thin film is conducted to produce an anode thin film with less capacity fading than that of a pure SnO2 film for a thin-film battery. The structural properties of the Sn/Li2O multilayer are examined. In addition, the electrochemical characteristics of the Sn/Li2O and pure SnO2 thin films are compared. X-ray diffraction and transmission electron microscopy measurements reveal a Sn crystalline peak only and a Sn–Li2O multilayer structure, respectively, in the Sn/Li2O thin film. A SnO2 thin film with a polycrystalline phase shows an irreversible side-reaction at 0.8V versus Li/Li+, an initial charge retention of about 29%, and poor cycleability in the cut-off voltage range from 1.2 to 0V versus Li/Li+. By contrast, no irreversible side-reaction is found in the Sn/Li2O multilayer composite thin film while there is an initial charge retention of 49% and better cycleability (more than twice) than that of pure SnO2 film after about 150 cycles. These results indicate that the Sn/Li2O multilayer composite thin film can be used for tin-based, thin-film, microbatteries and provide motivation to pursue fabrication of Sn–Li2O anode powder for bulk type batteries.