Transition metal ions (Mn2+, Cr3+, Fe2+/3+, V2+) as substitutional impurities in cubic crystals play an important role due to their influence on the magneto-optical properties of the virgin crystals. The optical and magnetic properties of commercial MgO(001) single crystals were investigated. The PL spectra of 3d impurity ions (Cr3+ and V2+) show narrow zero phonon lines with decay times in the range of milliseconds and a broad multiphonon sideband decaying in microseconds. The EPR study exhibits hyperfine components corresponding to Mn atoms and to V atoms located in orthorhombic symmetry. The intensity change of the EPR and PL spectra as well as the variation of the decay time with temperature can be explained by electron-spin lattice relaxation due to the Raman process. (C) 2011 Elsevier B.V. All rights reserved.