Magnesium vanadates are potentially important catalytic materials for the conversion of alkanes to alkenes via oxidative dehydrogenation. However, little is known about the active sites at which the catalytic reactions take place. It may be possible to obtain a significant increase in the catalytic efficiency if the effects of certain material properties on the surface reactions could be quantified and optimized through the use of appropriate preparation techniques. Given that surface reactivity is often dependent upon surface structure and that the atomic level structure of the active sites in these catalysts is virtually unknown, we desire thin film samples consisting of a single magnesium vanadate phase and a well defined crystallographic orientation in order to reduce the complexity and simplify the study of active sites. We report on the use of reactive rf sputter deposition to fabricate very highly oriented, stoichiometric Mg-3(VO4)(2) thin films for use in these surface analysis studies. Deposition of samples onto amorphous substrates resulted in very poor crystallinity. However, deposition of Mg-3(VO4)(2) Onto well-oriented, lattice-matched thin film "seed" layers such as Ti(0001), Au(lll), or Pt(lll) resulted in very strong preferential (042) crystallographic orientation (pseudohexagonal oxygen planes parallel to the substrate). This strong preferential growth of the Mg-3(VO4)(2) suggests epitaxial (single-crystal) growth of this mixed metal oxide on the underlying metal seed layer. The effects of the seed layer material, deposition temperature, and postdeposition reactive treatments on thin film properties such as stoichiometry, crystallographic orientation, and chemical interactions will be discussed.