Multiple angle of incidence spectroscopic ellipsometric data show that implantation of 150‐keV molybdenum ions into polished molybdenum laser mirrors causes microscopic surface smoothing, and that most of the microscopic roughness is removed by a fluence of 5×1015cm−2. Implantation of Au at 1 MeV significantly increases the microscopic roughness, and also changes the bulk optical properties. 3‐MeV Ni ion implantation causes only small changes in the surface and bulk properties. A dielectric film, probably a hydrocarbon, is found to condense on the mirrors in a laboratory atmosphere.