5 pages. Can also be found at : http://www.epjap.org/action/displayAbstract?fromPage=online&aid=8011580International audienceUsing electron-induced X-ray emission spectroscopy (XES), we have studied two Al/Ni periodic multilayers that differ only by their annealing temperature: as-deposited and annealed at 115°C. Our aim is to show that XES can provide further details about the chemistry at the metal-metal interface, in addition to what is obtained by X-ray diffraction. The distribution of valence states exhibiting Al 3p and Ni 3d character is determined from the analysis of the Al Kbeta and Ni Lalpha emission bands respectively. The multilayer emission bands are compared to those of reference materials: pure Al and Ni metals as well as Al3...