AbstractRare-earth doped wurtzite-type aluminum nitride (w-AlN) has great potential for high-efficiency electroluminescent applications over a wide wavelength range. However, because of their large atomic size, it has been difficult to stably dope individual rare-earth atoms into the w-AlN host lattice. Here we use a reactive flux method under high pressure and high temperature to obtain cerium (Ce) doped w-AlN single crystals with pink-colored luminescence. In order to elucidate the atomic structure of the luminescent centers, we directly observe individual Ce dopants in w-AlN using annular dark-field scanning transmission electron microscopy. We find that Ce is incorporated as single, isolated atoms inside the w-AlN lattice occupying Al substitutional sites. This new synthesis method represents a new alternative strategy for doping size-mismatched functional atoms into wide band-gap materials.