Local vibrational modes (LVMs) are reported for Mg‐doped GaN grown by metalorganic chemical vapor deposition. Hetero‐epitaxial layers of GaN:Mg, either as‐grown, thermally activated, or deuterated, were investigated with low‐temperature, Fourier‐transform infrared absorption spectroscopy. The as‐grown material, which was semi‐insulating, exhibits a LVM at 3125 cm−1. Thermal annealing increases the p‐type conductivity, as established with Hall effect measurements, and proportionally reduces the intensity of this LVM. Deuteration of the activated material creates a LVM at 2321 cm−1. The isotopic shift establishes the presence of hydrogen in the vibrating complex. The new LVMs are assigned to the stretch modes of the Mg–H and Mg–D complexes in GaN, with the vibrational frequencies indicative of a strong N–H bond as recently proposed from total‐energy calculations.