<p>Although the modified TiO₂ samples have been reported to catalyze the two-electron oxygen reduction reaction (2e^- ORR) to generate H₂O₂, the intrinsic activity and the specific role of the active species remain unclear, primarily due to the performance contributed by mixed carbon materials. In this work, we delve into the intrinsic selectivity of 2e^- ORR on pristine TiO₂, excluding the influence of any carbon-based materials. By subjecting pristine TiO₂, while excluding the influence of carbon-based materials, to electrochemical activation within the hydrogen reduction reaction regime, we observed a notable enhancement in H₂O₂% selectivity, rising from 56.6% to 67.2%. Our results demonstrate that the activation process proceeds in parallel with the reconstructions of the oxygen-deficient surface, transitioning from TiO_1.94 to TiO_1.78, accompanied by changes in the local electronic structure. These insights were revealed through multi-modal spectroscopy, including electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), hard X-ray photoelectron spectroscopy (HAXPES), and the high-resolution valence band (VB) spectra analysis via HAXPES. All these spectroscopic characterizations suggest that the surface reduction is likely driven by the formation of oxygen vacancies, while altered interactions between Ti and O lead to changes in the bulk electronic structures. These modifications collectively influence the selective oxygen reduction process and it is promising to be applicable for the comprehensive analysis of material structures and reaction mechanisms.</p>