Mixtures of ammonia and water are major components of the “hot ice” mantle regions of icy planets. The ammonia-rich ammonia hemihydrate (AHH) plays a pivotal role as it precipitates from water-rich mixtures under pressure. It has been predicted to form ionic high-pressure structures, with fully disintegrated water molecules. Utilizing Raman spectroscopy measurements up to 123 GPa and first-principles calculations, we report the spontaneous ionization of AHH under compression. Spectroscopic measurements reveal that molecular AHH begins to transform into an ionic state at 26 GPa and then above ∼69 GPa transforms into the fully ionic P¯3m1 phase, AHH-III, characterized as ammonium oxide (NH+4)2O2−.