Vanadium oxide has been deposited on TiO2 (washed anatase, 10 m2g−1; Degussa P-25, 55 ±3 m2g−1; Eurotitania, 46 m2g−1) by aqueous impregnation of (NH4)2[VO(C2O4)2] and by reaction with VOCl3, VO(OR)3 (R=iBu) and VO(acac)2 in organic solvents. Single applications of the last tree reagents form not more than a monolayer of vanadium oxide VOx, a monolayer being defined as 0.10 wt.% V2O5 per m2 of surface. When less than about four monolayers of VOx are present, there is in most cases only a single TPR peak: Tmax values, which increase with V2O5 content, are almost independent of the method used but vary slightly with the support (P-25 < Eurotitania < washed anatase). The 995 cm−1 band, characteristic of V&z.dbnd;O in V2O5, only appears when more than a monolayer of VOx is present. In the sub-monolayer region, VOx is best formulated as an oxohydroxy species bonded to two surface oxygens. As the V2O5 content is increased, layers of disordered V2O5 are formed on limited areas of the surface, but crystalline V2O5 only occurs, probably on top of the disordered V2O5, when the V2O5 content exceeds about four monolayers, and takes the form of acicular crystals exposing only planes perpendicular to the a and b axes.