A special self‐absorption effect of the Mg‐enriched surface of AlMg alloys is described for Al L2,3 emission spectra. In the light of these new considerations, the evaluation of the experimental data have to be modified and the earlier results in this field should be reevaluated. The problem is more general than this actual one, focusing attention on the complexity of the evaluation of emission spectra of alloys and compounds which have emission spectra, of the components nearby or overlapping each other.