In solids, strong repulsion between electrons can inhibit their movement and result in a “Mott” metal-to-insulator transition (MIT), a fundamental phenomenon whose understanding has remained a challenge for over 50 years. A key issue is how the wave-like itinerant electrons change into a localized-like state due to increased interactions. However, observing the MIT in terms of the energy- and momentum-resolved electronic structure of the system, the only direct way to probe both itinerant and localized states, has been elusive. Here we show, using angle-resolved photoemission spectroscopy (ARPES), that in V2O3, the temperature-induced MIT is characterized by the progressive disappearance of its itinerant conduction band, without any change in its energy-momentum dispersion, and the simultaneous shift to larger binding energies of a quasi-localized state initially located near the Fermi level.