The regularities of photo- and thermoluminescence processes in submicrosized AlN crystals with cationic deficiency after UV excitation are studied. The observed emission spectra are a superposition of Gaussian bands with maxima at 3.0 and 2.5 eV. The indicated spectral features are due to electronic transitions involving ON impurity and (VAl –ON) oxygen-vacancy complexes. According to a quantitative analysis in the framework of the general order kinetics, carrier capture centers based on VN nitrogen vacancies have an activation energy of 0.45 eV and are responsible for the forming of the thermally stimulated luminescence with maximum at a temperature of 345 K.