Characterization of the α-zirconium phosphates 1-D2Oh and 1-D2Oh/dr, partially hydrolyzed with D2O, by powder X-ray diffraction, scanning electron microscopy, and multinuclear solid-state NMR techniques led to an unprecedented observation of D3O+ ions located on the surface and stabilized by hydrogen bonds. These ions are formed after the surface phosphate groups have been lost.