Metallic first mirrors (FMs) are foreseen to play a crucial role for all optical diagnostics in ITER. It is highly important for the FMs to maintain a good reflectivity both in erosion and deposition zones in the harsh ITER environment. Molybdenum mirrors, which are important candidates for the FMs, exhibit a reflectivity spectrum different from that of bulk molybdenum after exposure to low temperature (4–5 eV) deuterium plasma. This difference is mainly due to the presence of deuterium and deuterium-induced defects in the metal. The results presented show that these reflectivity changes are similar for single and nanocrystalline molybdenum mirrors. Moreover, exposure of magnetron sputtered nanocrystalline molybdenum films to deuterium plasma revealed that after a certain deviation of the spectrum has been reached, the reflectivity remains constant upon further exposure. Exposures were carried out in a range of fluences corresponding to up to 18 ITER discharges in equatorial ports and 38 discharges in the upper ports in the first wall positions. Constant conditions of −200 V bias and 150 °C temperature were maintained on the samples. Further exposures performed in a tokamak result in reflectivity changes that are comparable to those obtained with deuterium plasma exposure. No mechanical damage, such as blistering and increase in roughness, is observed on the coated molybdenum films upon any of the mentioned exposures. The complex permittivity of the exposed molybdenum is determined from ellipsometry measurements and corroborated with core and valence level photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy and surface resistivity measurements.