In order to shed light on the striking difference between the electrons trapped at the SACinduced states in a-TiO2(400)-V SA and in a-TiO2-Cu SA with respect to their reactivity with dioxygen, we performed a set of DFT calculations (for details see Supporting Information, 3. Computational details). The (101) surface of anatase TiO2 was used in calculations as it is the most stable and most prevalent facet in small TiO2 crystallites present in our materials. The results are summarized in Figure . Grafting of Cu(II) and vanadate species onto the anatase (101) surface induces, in both cases, the formation of highly localized intragap states.