We studied the deposition of Au, In, Ag, and Al overlayers onto clean-cleaved GaTe(001) surfaces at room temperature by x-ray photoelectron spectroscopy. Gold and In overlayers did not produce evidence of chemical reactions, and neither with cation nor anion outdiffusion. Gold overlayers exhibited no evidence of island formation and a layer-by-layer overlayer coverage. The deposition of In revealed the presence of clustering for a metal thickness higher than 6 Å. On the other hand, the deposition of Al lead to an exchange reaction with a metalliclike Ga phase separation. Core level analysis of the Ag–GaTe interface revealed no noticeable change of the shape of the peaks. The dependence of the peak intensities on overlayer thickness showed an initial layer-by-layer coverage until 1.8 Å, followed by a clustering growth mode. From about 3.7 Å Ag thickness, significant Te outdiffusion was observed.