Nominally anhydrous minerals such as olivine contain trace amounts of water and may accommodate the entire water budget of the upper mantle. Here we report for the first time synthetic olivines, crystallized experimentally under upper mantle conditions, that reproduce the most common and intense infrared hydroxyl stretching bands (at 3572 and 3525 cm−1) observed in spinel peridotite mantle olivines. These bands arise from water accommodated at point defects associated with the trace element Ti, and we suggest that this is the most important defect site in the shallow upper mantle. Additional hydrated defects may occur at higher pressures. We also identify bands related to water associated with Fe3+; these are unlikely to reflect equilibrium with the mantle, and indicate water incorporation during exhumation or retrogression. Water must be present at the defect site appropriate for the mantle, at the conditions of interest, for partitioning, seismic wave speed, and deformation experiments on hydrous olivine to be relevant.