The catalytic performance in the oxidehydrogenation (ODH) of propane of vanadium oxide catalysts supported on gallium oxide, VOx/Ga2O3, with vanadium coverages lower or near the theoretical monolayer has been studied as a function of the vanadium content and compared with those of other known effective V-M-O (M = Mg, Ca) catalysts. Catalyst activity was very high and increased with the increase of vanadium loading in the range studied, while the selectivity trend was similar for the studied catalysts, excepting that with the lower V content. Fr-Raman and V-51 solid state NMR spectroscopies show that for coverages below the theoretical monolayer vanadium atoms are in tetrahedral co-ordination either in isolated or polymeric species, while the onset of vanadia formation is detected above that coverage. Interestingly, these catalysts show an one order of magnitude higher area-specific rate, similar initial olefin selectivity and slightly higher selectivity decrease with the increase of conversion than the best VMgO catalyst. This is due to the high intrinsic activity of isolated tetrahedral vanadium species. The combination of these factors produces an enhanced olefin productivity of V-Ga-O catalysts.