The electronic structure of the TiO2 (110)-(1 × 2) surface has been studied by means of angular resolved ultraviolet photoemission spectroscopy (ARUPS). The valence band dispersion along the high symmetry surface directions, [001] and [1–10], has been recorded. The experimental data show no dispersion of the band-gap Ti 3d states. However, the existence of dispersive bands along the [001] direction located at about 7 eV below the Fermi level is reported. The existence of two different contributions in the emission from the defects-related state located in the gap of the surface is univocally shown for the first time.