We use soft x‐ray photoemission spectroscopy to study the Ga/GaAs and Mn/GaAs interfaces formed at room temperature (RT) and at low temperature (LT=80−100 K). The LT Ga/GaAs interface exhibits the strongly inhibited clustering observed at other nonreactive metal/GaAs interfaces. The Mn–GaAs reaction is slowed somewhat. At both interfaces, the effect of temperature onEFmovement is in accord with the trends previously set: initial band bending onn‐GaAs is slowed at LT, whereas band bending onp‐GaAs is not affected significantly. For both Ga and Mn/GaAs,EFmovement at low coverages is consistent with the explanation proposed for thespand noble metals: introduction of donor states from, e.g., the specific adsorbate levels. Studies of the noble metal interfaces with GaAs have showed that the establishment of the finalEFposition is related to the appearance of metallicity at the interface; Mn/GaAs provides direct evidence for that interpretation.