The atomic-scale structure, relative stability and infrared spectroscopic properties of OH defects in corundum (α-Al 2 O 3) are theoretically investigated at the density functional theory level. Comparison with experimental data makes it possible to assign most of the narrow bands observed between 3150 and 3400 cm −1 in natural and Ti-or V-doped synthetic corundum to specific defects. These defects correspond to the association of one OH group with an Al vacancy and M 4+ for Al 3+ substitutions in neighboring sites. The OH group is located in the large oxygen triangle forming the base of the vacant Al site. Models of interstitial proton associated with a nearby Mg 2+ for Al 3+ substitution are consistent with the broad band observed at 3010 cm −1 in Mg-doped corundum. Its is also suggested that two weaker OH-stretching bands observed in nominally pure synthetic corundum at 3163 and 3209 cm −1 could be associated with intrinsic defects combining an Al and an O vacancy. These results highlight the importance of defect clustering in the high-temperature incorporation of hydrogen in nominally anhydrous minerals.