The CIGSe/In2S3 interface is known to be highly diffuse because of the migration of Cu from the CIGSe into the In2S3. Most of the analytical techniques allowing the determination of composition profiles throughout this interface involve ion etching either during the samples preparation or during data acquisitions. In the present work, we have explored the potential of the Raman scattering for the characterization of such interfaces. This technique is non destructive and provides information on both the composition and the structure of the materials that are probed. Three CIGSe/In2S3 structures have been investigated: the parameter varying being the substrate temperature during the In2S3 deposition. For the first time we could demonstrate that at high temperature, the CuInS2 Cu-Au phase is formed at the CIGSe/In2S3 interface. Furthermore, the thickness of the ordered defect compound at the CIGSe surface increases with the deposition temperature. All of the new knowledge collected during this work shows the relevance of using the Raman scattering technique for the characterization of the CIGSe/In2S3 interface. (C) 2010 Elsevier B.V. All rights reserved.