Aluminum oxynitride (AlON), which can be regarded a nitrogen-stabilized cubic gamma-Al2O3, has attracted attention in terms of its good mechanical, chemical, and optical stability. Because of its optical inertness, however, photoluminescence (PL) emission from nominally pure AlON has not been carefully investigated and evaluated. In this work, we prepared visibly luminescent AlON by nitridation of gamma-Al2O3 under N-2 atmosphere without adding aluminum nitride (AlN) using a high-frequency induction heating unit. The resulting AlON exhibits a broad PL emission in the blue/green spectral region under excitation with light of similar to 260 nm. In the luminescent AlON sample, the excitation and emission events will occur at different sites; the electron transfer from the excitation site to the emission site is preceded by the radiative recombination process. It has also been found that the PL peak wavelength shows an anomalous blue shift by similar to 50 nm with increasing temperature from 78 to 500 K. The observed temperature dependent PL characteristics are governed by thermalization among multiple emitting levels. Aluminum vacancies and oxygen vacancies, both of which are introduced into the crystalline lattice during nitridation without the presence of AlN, are very likely candidates for the excitation and emission centers, respectively. Hence, the present direct nitridation method provides a simple and effective way to add an additional optical functionality to otherwise optically inactive AlON.