Titanium dioxide (TiO2) has rich physical properties with potential implications for both fundamental physics and new applications. To date, the main focus of applied research is to tune its optical properties, which is usually done via doping and/or nanoengineering. However, understanding the role of d electrons in materials and possible functionalization of d-electron properties are still major challenges. Herewith, within a combination of an innovative experimental technique, high-energy optical conductivity, and state-of-the-art 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 TiO2 films. It is surprisingly robust and related to strong electron-electron and electron-hole interactions. The d- and f-orbital 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 TiO2 films and on the possibility of tuning electronic properties by Ta substitution. © 2016 American Physical Society.