Isolated and uniform V5+-oxo species were grafted onto H-ZSM5 at V/Al-f ratios of 0.2-1 via sublimation of VOCl3 precursors. These methods avoid the restricted diffusion of solvated oligomers in aqueous exchange, which leads to poorly dispersed V2O5 at external zeolite surfaces. Sublimation methods led to stable and active V-ZSM5 catalysts for oxidative dehydrogenation (ODH) reactions; they led to an order of magnitude increase in primary C2H6 ODH rates compared with impregnated ZSM5 catalysts at similar V/Alf ratios and showed similar activity to impregnated VOx/Al2O3. The structure of grafted V5+-oxo species was probed using spectroscopic and titration methods. Infrared spectra in the OH region and isotopic exchange of D-2 with residual OH groups showed that exposure to VOCl3(g) at 473 K led to stoichiometric replacement of HI by each (VOCl2)(+) species. Raman spectra supported by Density Functional Theory electronic structure and frequency calculations showed that, at V/Alf < 0.5, hydrolysis and subsequent dehydration led to the predominant formation Of (VO2)(+) species coordinated to one Al site with single-site catalytic behavior (0.7-0.9 X 10(-3) Mol C2H4 V-1 s(-1), 673 K). At higher V/Alf ratios, simulation of extended X-ray absorption fine structure spectra indicated that V2O42+ dimers coexisted with VO2+ monomers and led to an enhancement in ODH rates as a result of bridging V-O-V (1.3 x 10(-3) mol C2H4 V-1 s(-1)). These V5+-oxo species form via initial reactions between VOCl3(g) and OH groups to form HCl(g), hydrolysis of grafted (VOCl2)(+) to form HCl(g) and (VO(OH)(2))(+), and intrarnolecular and intermolecular condensation to form monomers and dimers, respective with the concurrent evolution of H2O. Raman and X-ray spectroscopies did not detect crystalline V2O5 at V/Alf ratios of 0.2-1, but V2O5 crystals were apparent in samples prepared by impregnation or physical mixtures Of V2O5/H-ZSM5. Framework Al atoms and zeolite crystal structures are maintained during VOCl3 treatment and subsequent hydrolysis; Al-27 and Si-29 MAS NMR showed that these synthetic protocols removes < 10% of the framework Al atoms (Al-f).