In this work, structural and morphological changes in composite sulfur electrodes were studied due to their cycling in rechargeable Li-S cells produced by Sion Power Inc. Composite sulfur cathodes, comprising initially elemental sulfur and carbon, undergo pronounced structural and morphological changes during discharge-charge cycles due to the complicated redox behavior of sulfur in nonaqueous electrolyte solutions that contain Li ions. Nevertheless, Li-S cells can demonstrate prolonged cycling. To advance this technology, it is highly important to understand the evolution of the structure and morphology of sulfur cathodes as cycling proceeds. High resolution scanning and tunneling microscopy, scanning probe microscopy, and Raman spectroscopy were used in conjunction with the electrochemical measurements. A special methodology for slicing composite sulfur electrodes and their cross sectioning and depth profiling was developed. The gradual changes in the structure of sulfur cathodes due to cycling is described and discussed herein. Important phenomena include changes in the surface electrical conductivity of sulfur electrodes and pronounced morphological changes due to the irreversibility of the sulfur redox reactions. Based on the observations presented in this work, it may be possible to outline guidelines for improving Li-S battery technology and extending its cycle life. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3479828] All rights reserved.