Supported vanadium oxide species are active catalysts for the selective, oxidative conversion of hydrocarbons to useful chemicals. Both the catalytic vanadium oxide and the supporting oxide were synthesized by ALD on high surface powders and anodic aluminum oxide (AAO) nanoliths. The nanoliths were prepared by anodic oxidation of aluminum. 1 nm of ALD aluminum oxide acts as the support for vanadium oxide loaded by 1 to 18 ALD cycles of vanadyltri-isopropoxide/ H202. Ultraviolet-visible absorption edges red shift as the vanadia loading increases. The edge energy of 1-cycle ALD VOx corresponds to isolated, tetrahedral VO4 in agreement with Raman spectroscopy. V-O-V bonds form with additional cycles producing a gradual increase in VO x domain size. Reaction rate coefficients for the oxidative dehydrogenation of cyclohexane show increased overall activity in the high loading catalysts but a higher specific activity in the low loading catalysts for cyclohexene formation.