Engineered solid supports for vanadium catalysts were prepared by atomic layer deposition (ALD) of alumina and titania layers on silica. The thickness of these layers was found to have a significant effect on the structure of the solid supports, their interaction with vanadia, and their catalytic performance with regard to oxidative dehydrogenation of propane. The catalytic performance of supported vanadia catalysts is reported for both ALD-engineered and conventional solid supports (gamma-Al2O3 and TiO2). The analysis results indicated that the engineered supports behave as a separate phase rather than a cross between the base silica and the deposited alumina or titania.