Defects in ammonothermal GaN have been studied using a monoenergetic positron beam. Through measurements of Doppler broadening spectra of the annihilation radiation, the major defect species was identified as a Ga vacancy coupled with impurities such as oxygen and/or hydrogen. Those defects were found to be stable even after annealing at 1000°C. The shape parameter S for the Doppler broadening spectrum corresponding to positron annihilation at the surface was found to be decreased by illumination within energy ranges of 1.5–2.6eV and 3.2–3.6eV. This phenomenon is attributed to the suppression of recombinations between holes and electrons due to trapping centers, which can hold electrons for a long time, and a resultant accumulation of holes at the surface. Recovery of the S value required almost one day, but it was shortened by the annealing at 1000°C.