Titanium dioxide (TiO) has rich physical properties with potential implications in both fundamental physics and new applications. Up-to-date, the main focus of applied research is to tune its optical properties, which is usually done via doping and/or nano-engineering. However, understanding the role of -electrons in materials and possible functionalization of -electron properties are still major challenges. Herewith, within a combination of an innovative experimental technique, high energy optical conductivity, and of the state-of-the-art {\it ab initio} electronic structure calculations, we report an emerging, novel resonant exciton in the deep ultraviolet region of the optical response. The resonant exciton evolves upon low concentration Ta-substitution in anatase TiO films. It is surprisingly robust and related to strong electron-electron and electron-hole interactions. The - and - orbitals localization, due to Ta-substitution, plays an unexpected role, activating strong electronic correlations and dominating the optical response under photoexcitation. Our results shed light on a new optical phenomenon in anatase TiO films and on the possibility of tuning electronic properties by Ta substitution.

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