We use ultra-high vacuum scanning tunneling microscopy (UHV–STM) to probe, at the atomic level, the structure of mass-selected isolated V 1, V 2, VO and VO 2 clusters deposited on rutile TiO 2(110) by ion soft landing. All four species interact differently with the TiO 2 surface and the ultimate binding site and configuration strikes a balance between the gas-phase structure and the ligation of this cluster by the TiO 2 surface. Our results show that vanadium atoms prefer to bind in the upper threefold hollow sites on the surface and have a slight tendency to pair along the [1–10] direction, while vanadium dimers bind to the surface oriented along the [001] direction exclusively. VO clusters bind with the vanadium atom in the upper threefold hollow site and with the oxygen atom bound to an adjacent fivefold coordinated Ti atom (5c-Ti). The VO 2 cluster also binds with the vanadium atom in the upper threefold hollow site and with both oxygen atoms bound to adjacent 5c-Ti atoms or with only one oxygen bound to the surface and the other directed out of the plane of the surface.