We investigated the interaction of extremely thin (less than 10 nm) crystalline gold and rhodium films with amorphous silicon by transmission electron microscope in situ annealing. In thin Au/Si bilayers an amorphous phase with a diffraction peak at d ≂ 0.226 nm is formed by thermal annealing between 150 and 200 °C. Depending on the thickness and composition, silicon sputtered onto thin gold films leads to the formation of a layer of amorphous silicon and a partially amorphous Au-Si layer during deposition. The silicon layer crystallizes by itself at temperatures as low as 150 °C, and at 300 °C the amorphous Au–Si layer crystallizes into a metastable gold silicide (for silicon-rich compositions). In Rh/Si bilayers an amorphous Rh–Si phase is formed by annealing to 300 °C and can be detected by electron diffraction for a rhodium thickness of less than 5 nm and compositions with more than 50% Si if completely reacted. Above 300 °C the amorphous Rh-Si crystallizes preferentially in the cubic form of RhSi for intermediate silicon compositions and in the orthorhombic form of RhSi for high silicon compositions. Excess amorphous silicon is not found to have a lowered crystallization temperature when in contact with the amorphous Rh-Si alloy, and crystalline silicon is only observed above 730 °C together with the cubic and/or orthorhombic RhSi. In Rh/Si bilayers with a thicker rhodium layer, no formation of an amorphous phase was observed on annealing; instead crystalline Rh2Si forms during annealing above 300 °C.