A series of isothermal annealing experiments have been performed in the range 790–920°C under N2 flow in order to study the deuterium out-diffusion kinetics of Mg-doped GaN grown on sapphire under deuterated ammonia. The deuterium concentration was measured by SIMS analysis before and after each annealing step. The kinetics closely follow a first-order law. The activation energy related to the deuterium out-diffusion process is 3.1 eV. In addition, deuterium effusion measurements were performed measuring the molecular HD flux while the specimens were annealed in ultra high vacuum with a linear heating rate. In contrast to SIMS, this method detects the species that migrated out of the sample. Effusion peaks of the HD flux at 360 and 490°C are attributed to the fragmentation of adsorbed CHxDy complexes. The molecular HD flux starts increasing at 800°C which is the onset of the GaN decomposition and has its maximum at 920°C. This HD flux is accompanied by the desorption of H and D containing radicals and molecules desorbing above 900°C.