We prepared vanadia–titania model catalysts with V(+5) oxidation state by sublimating V₂O₅ powder onto clean anatase TiO₂(101) [a-TiO₂(101)]. The V₂O₅/a-TiO₂(101) model catalysts with V₂O₅ in the sub-monolayer coverage range were studied with scanning tunneling microscopy, lab-source X-ray photoelectron spectroscopy, and synchrotron-radiation X-ray photoelectron spectroscopy. On freshly prepared V₂O₅/a-TiO₂(101) samples, we find well-dispersed V₂O₅ clusters as the smallest species, together with larger particles of V₂O₅ stoichiometry. Upon vacuum-annealing at ∼500 K, small V₂O₅ clusters agglomerate into larger particles. Upon vacuum-annealing at ∼700 K, vanadia reduces and, eventually, disappears from the surface via V diffusion into the bulk. The V₂O₅/a-TiO₂(101) model catalyst can be hydroxylated by an ice-assisted preparation. We find evidence for OH groups located at the V₂O₅/a-TiO₂(101) interface as well as at the a-TiO₂(101) support.