The structure and morphology of CaF2/Si(111) and Ge/CaF2/Si(111) layered structures with film thicknesses in the range of very few nanometers has been studied with synchrotron-based radiation. While the CaF2 film is grown via molecular beam epitaxy, the Ge film is fabricated by surfactant enhanced solid phase epitaxy with Sb as surfactant. The CaF2 film forms two laterally separated phases of relaxed CaF2 and pseudomorphic CaF2, respectively, although the film thickness is very homogeneous. The Ge film is completely relaxed and forms A-oriented parts as well as B-oriented parts, due to twinning. In spite of the large surface roughness of the Ge film, it completely wets CaF2/Si(111) also after annealing at 600 °C, due to the application of Sb during the annealing process.