Low-energy electron diffraction I/V analyses reveal that Mn thin films deposited on Ag͑001͒ at room temperature form substitutional, ordered, bilayer Mn 50 Ag 50 surface alloys. The Mn atoms in this structure have local magnetic moments of considerable value, as judged from the Mn 3s core level spectra; these local magnetic moments of Mn are effective in the formation of the ordered surface alloy. Ab initio total energy calculations have been done and the results confirmed the experimental observations.