Yb silicides have been grown epitaxially on the Si(111) surface using solid‐state epitaxy with annealing to 400 ° C. The amount of deposited Yb was varied from parts of a monolayer to films being about 40 monolayer thick. Auger‐ and photoelectron spectroscopy showed that Si segregates into the Yb overlayer at room temperature and that a strong reaction occurs during annealing to 400 ° C leading to the formation of thick silicides. The epitaxial silicides showed a 1×1 or a √3×√3 low‐energy electron diffraction pattern depending on the detailed preparation procedure. The composition of the silicide was found to be YbSi2−x.