We have used Raman spectroscopy, large- and small-angle x-ray diffraction spectroscopy of sputter-deposited, vacuum-annealed, soft x-ray Mo/Si thin-film multilayers to study the physics of silicide formation. Two sets of multilayer samples with d-spacing 8.4 and 2.0 nm have been studied. Annealing at temperatures above 800 °C causes a gradual formation of amorphous MoSi2 interfaces between the Si and Mo layers. The transition from amorphous to crystalline MoSi2 is abrupt. The experimental results indicate that nucleation is the dominant process for the early stage and crystallization is the dominant process after nucleation is well advanced. In the thicker multilayer, a portion of the silicon crystallizes during annealing and a strong Raman signal is observed. An advantage of Raman spectroscopy is that the Raman signal of the silicide is observed even before the presence of MoSi2 can be seen using x-ray diffraction. This study indicates that Raman spectroscopy is an effective technique for characterizing the formation of crystalline silicides.