The growth by molecular beam epitaxy of GeTe thin films on highly lattice-mismatched Si(111) substrates is reported. In situ reflection high-energy electron diffraction and quadrupole mass spectrometry were employed to monitor the growth process in real time and tune the deposition conditions. Epitaxy was achieved in a window of substrate temperatures between 220 and 270 °C, using a Ge/Te flux ratio of ∼0.4. Extensive ex situ X-ray diffraction characterization showed that the epitaxial layers crystallize in the rhombohedrally distorted rocksalt structure α-GeTe, with orientation relationships to the substrate α-GeTe ‖ Si and α-GeTe〈100〉 ‖ Si〈〉. ω-scans of the α-GeTe(000n) reflections (n = 3, 6, 9) exhibit a full width at half maximum between 10 and 20 arcsec, indicating small mosaicity. However, a large twist is observed (∼14°), pointing to the presence of rotational domains. In addition, the layer matrix is affected by twinning. The epitaxial films exhibit a slight tensile in-plane strain, which might be due to the difference in thermal expansion coefficients between α-GeTe and Si, and/or small deviation from stoichiometric composition, i.e., vacancies in the Ge sub-lattice.