A molecular‐orbital energy‐level diagram is constructed and used to interpret the metal‐ionLII,IIIx‐ray emission and absorption spectra from the oxides, nitrides, carbides, and borides of titanium and vanadium. It is shown that the MO model provides a more accurate description of the experimental results than did the ionic model and crossover transition theory. Specific electronic transitions are assigned to spectral components. Anomalous emission peaks which fall on the low‐energy side of the mainLIIIband are found to originate in molecular orbitals which are primarily associated with ligand 2pand 2slevels.