Thin-film Cu6Sn5 anodes were created using a radio frequency magnetron sputtering technique. Several films were studied demonstrating different compositional variables, namely, (i) as-deposited, nanocrystalline Cu6Sn5 on stainless steel, (ii) annealed Cu6Sn5 on stainless steel, and (iii) Cu6Sn5/Pt film electrodes. The annealed Cu6Sn5 films showed enhanced grain growth compared to the as-deposited samples, were found to have higher crystallinity, and exhibited a lower lithium cycling capacity than the nanocrystalline samples. Films incorporating a Pt underlayer between the current collector and the Cu6Sn5 film were evaluated and showed a 30% higher cycling capacity than the annealed samples or typical bulk laminates. Understanding the interaction between the interlayer and the displaced copper is postulated to be an important variable in extending cycle life. (C) 2008 The Electrochemical Society.