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We attempt to grow 20‐nm‐thick layers of Sb and Ge as well as periods of (20 nm Sb/20 nm Ge) layers on muscovite (a special form of mica) by van der Waals epitaxy under different growth conditions. The growth process was in situ investigated by reflection high‐energy electron diffraction and Auger electron spectroscopy. Epitaxial Sb layers could be obtained even at cold substrates (mica or polycrystalline Ge layers). It was not possible to grow monocrystalline Ge layers by van der Waals epitaxy. Only a formation of oriented Ge grains could be observed at higher temperatures.