The alloying reaction in a thin nickel film deposited on a GaAs substrate was investigated using microprobe Auger spectroscopy, reflection high energy electron diffraction and transmission electron diffraction. A nickel film reacts with the substrate above 200°C to form a metastable hexagonal reaction product with the composition Ni:Ga:As = 2:1:1, which is monocrystalline with the orientation relation 〈0001〉 hexagonal // 〈111〉 GaAs and 〈11 2 0〉 hexagonal // 〈110〉 GaAs. Above 400°C the metastable reaction product decomposes into NiAs and β-NiGa, both of which are also monocrystalline with the same orientation relation as the metastable reaction product. The role of nickel in GaAs contact systems is explained by the high reactivity of nickel with GaAs in the solid-solid phase.