We have combined synchrotron radiation photoemission (PES), X-ray photoelectron diffraction (PED) and low-energy electron diffraction (LEED) to examine the formation of the Ag/Si(1 1 1)-(7×7) interface, throughout a wide silver coverage range. All studied silver films gave rise to a fcc phase with their principal crystallographic axes parallel to the substrate and a [1 1 1] orientation perpendicular to the surface. Angular-scanned PED of the Ag 4p core level showed the formation of well-ordered Ag islands, with the presence of two well-defined domains, both for 6 and 30 ML films. The two domains were rotated 60° from each other and appeared in a 60/40 proportion.