Powdered and single‐crystal MgO, implanted with 60 keV He, Ar, Fe, and Cr ions, have been examined by laser‐stimulated photoluminescence. The photoluminescence from damage‐related defects, centered at 14 350 cm−1, and from MgO : Cr3+zero‐phonon line at 14 325 cm−1are discussed. The annealing behavior of the introduced defects and impurities is characterized by the room‐temperature and liquid‐nitrogen‐temperature photoluminescence observed before and after 1 h anneals of 325, 600, and 900 °C. A comparison is made between the ion‐implanted and the impurity‐grown systems. Speculation is made on the nature of the damage‐related defects as the source of the broad emission centered at 14 350 cm−1. Correspondence to the previously observed absorption band at 17 420 cm−1is made.