Epitaxial growth of Si and Ge films onto silicide/Si and fluoride/Si structures has been reviewed. Growth conditions of epitaxial silicide films such as Pd2Si, CoSi2, and NiSi2films on Si substrates, as well as heteroepitaxial Si/CoSi2/Si structures, are presented. Crystalline quality and structural properties of the films have been analyzed by Rutherford backscattering and channeling spectroscopy, transmission electron microscopy, optical microscopy, and x‐ray diffraction analysis. Growth conditions of fluoride films such as CaF2, SrF2, and BaF2films on Si substrates are also presented. For the growth of Si and Ge overlayers on the fluoride/Si structure, the lattice matching condition between the semiconductor and fluoride films has approximately been satisfied by use of pure and mixed fluoride films.