Room temperature deposition of Ag on InSb(111) is known to lead to three-dimensionalclustering, without long-range crystalline order. We show by means of angle-resolvedphotoemission that ‘two-step’ growth in which the films are annealed to roomtemperature after low temperature deposition results in the formation of Ag films whichare epitaxial, atomically flat, and display a quasi-discrete quantum well bandstructure. Core level analysis highlights different chemical interactions between thesubstrate and deposited materials for room temperature and ‘two-step’ Ag growth.