Novel short-period MnF<sub>2sub>–CaF<sub>2sub> superlattices (SLs) on Si(111) substrates have been grown by molecular beam epitaxy. The thickness of a MnF<sub>2sub> layer was 1–3 molecular layers. Reflection high-energy electron diffraction studies indicated the fluorite type of crystal structure of these layers. Fluorescent extended X-ray absorption fine structure measurements supported this observation. Atomic force microscopy measurements showed a flat surface morphology of the SLs. X-ray diffraction measurements revealed well-pronounced superstructural reflections. The width of their ω-curve did not exceed 2.5 arc min, which indicated a good crystal quality of the SLs.