Oxygen vacancies often determine the electronic structure of metal oxides, but existing techniques cannot distinguish the oxygen-vacancy sites in the crystal structure. We report here that time-resolved optical spectroscopy can solve this challenge and determine the spatial locations of oxygen vacancies. Using tungsten oxides as examples, we identified the true oxygen-vacancy sites in WO2.9 and WO2.72, typical derivatives of WO3 and determined their fingerprint optoelectronic features. We find that a metastable band with a three-stage evolution dynamics of the excited states is present in WO2.9 but is absent in WO2.72. By comparison with model bandstructure calculations, this enables determination of the most closely neighbored oxygen-vacancy pairs in the crystal structure of WO2.72, for which two oxygen vacancies are ortho-positioned to a single W atom as a sole configuration among all O─W bonds. These findings verify the existence of preference rules of oxygen vacancies in metal oxides
