Temperature-dependent photoluminescence (PL) of titanium oxide (TiO2) shows an evolution of blue emission when exposed to 50 keV Ar+ ions. The origin of observed PL has been examined by X-ray absorption near-edge spectroscopy (XANES) at Ti-K,L and O-K edges, revealing the reduction of ligand field splitting owing to the formation of oxygen vacancies (OVs) by destroying TiO6 octahedral symmetry. Detailed PL and XANES analyses suggest that the fluence (ions/cm2) dependent increase in OVs not only boosts the conduction electrons but also increases the density of holes in localized self-trapped exciton (STE) states near the valence band. Based on these observations, we propose a model in which doped conduction electrons are recombining radiatively with the holes in STE states for blue light emission. © 2017 American Chemical Society.