<p>This article reports a facile, fluoride-free hydrothermal synthesis of highly active anatase TiO₂ nanocrystals with a high percentage of (001) facets. These (001)-faceted TiO₂ catalysts exhibit remarkable activity in the visible-light-induced oxidation of various amines, including aliphatic, primary, secondary amines, and N-heterocycles, as well as in amine cross-coupling reactions under ambient air conditions. The high reactivity is attributed to the formation of a surface complex between the amine and the TiO₂ (001) facet, which acts as a visible-light sensitizer, modifying the band structure of TiO₂ and facilitating efficient charge separation and subsequent oxidation processes. Notably, these reactions proceed effectively under visible light irradiation despite the inherent UV-light absorption of TiO₂. The catalyst demonstrates excellent recyclability with minimal activity loss over six cycles and can be utilized for the gram-scale synthesis of imines, making it a promising and sustainable approach for amine oxidation reactions.</p> Graphical Abstract <p></p>