Abstract The ZnS:Mn, Mg powder is fabricated by self-propagating high-temperature synthesis with the simultaneous introduction of Mn and Mg impurities. It is found that the simultaneous introduction of Mn and Mg impurities leads to the nonuniform distribution of manganese forming regions with a lower and higher Mn concentration. In the latter case, the manganese ions form paramagnetic clusters. At the same time, numerous centers of self-activated luminescence form in the synthesized ZnS:Mn, Mg due to mechanical stress and lattice strain. Additional annealing leads to a more uniform Mn distribution in the formed ZnS:Mn, Mg phosphor, which is accompanied by an increase in the intensity of the manganese photoluminescence band and quenching of the self-activated luminescence band.