In order to extend the comparison of the initial stages of Schottky barrier formation to different surfaces of III–V semiconductors, we present here an investigation with low‐energy electron diffraction, Auger electron spectroscopy, and ultraviolet photoemission spectroscopy of In– and Ag–GaSb(100) interfaces at room temperature and after annealing. The initial GaSb surfaces exhibit a (3×2) structure. The low‐coverage growth of In and Ag is essentially two dimensional. It is followed by substantial islanding (In) especially after annealing. Band bending measurements show no significant movement of the Fermi level from its initial position near the valence band maximum.