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Nucleation of GaAs on Si in molecular‐beam epitaxy is studied by Auger electron spectrometry and reflection high‐energy electron diffraction. It is shown that, if growth is initiated at room temperature and if a GaAs equivalent thickness of ∼15 Å is deposited on Si, an amorphous, nonstoichiometric layer is obtained which covers completely the substrate surface. Stoichiometry and monocrystallinity can be restored by thermal annealing at 350 °C by a solid‐phase epitaxy mechanism. Under such conditions the initial stages of GaAs/Si growth can then proceed via two‐dimensional nucleation, instead of the three‐dimensional mode observed at higher growth temperatures.