Structures consisting of alternate layers of Mo/Ti and W/Ti have been sputter deposited on Si(100) substrates and their annealing behavior has been studied using Auger sputter profiling. The anneals were performed under typical processing conditions. Two major driving forces control the observed reactions: the silicidation of the metals and the oxidation of Ti. The prevalence of one of them depends both on the structure of the as‐deposited film and on the annealing temperature. In the case where silicidation prevails a multisilicide layer is formed, with no alteration with respect to the initial disposition order of the metal films. Intermixing between the reacted layers starts to be observed at 900 °C. The behavior of common contaminants such as oxygen and carbon has been studied.