Alloys of Si with elements such as Sn, Ag, or Zn may exhibit large specific and volumetric capacities when cycled electrochemically vs lithium. Combinatorial films of Si1-xMx in the range 0 < x < similar to 0.60 have been prepared by magnetron sputtering, where M is Sn, Ag, or Zn. These films have been analyzed for structure, composition, and electrochemical performance. The electrochemical performance of the film is found to be dependent on the element M as well as the amount, x, of the element in the film. The three Si-based binary systems are compared in terms of phases formed, amorphous vs crystalline structure, and capacity retention. It is found that electrodes which remain as a single amorphous phase during insertion and removal of Li exhibit superior capacity retention as compared to electrodes that form multiple or crystalline phases. (c) 2005 The Electrochemical Society. [DOI: 10.1149/1.2140607] All rights reserved.