Pure and mixed magnesium molybdate phases (MoO3, MgMoO4, and MgMo2O7) have been examined for the oxidative dehydrogenation reaction of propane. The results are very sensitive to the stoichiometry and method of preparation. The catalysts exhibiting superior activity and selectivity are characterized by a unique temperature-programmed reduction peak that is not present for the poorly active or selective catalysts. Mixtures of MgMoO4 and MoO3 or MgMoO4 and MgMo2O7, materials that perform poorly by themselves, show significant improvements in performance upon heating. The solid-state interactions leading to these improvements correspond to the appearance of the characteristic reduction peak. The results suggest that the beneficial synergistic effects seen with mixtures of inactive phases are due to formation of a new phase or species, rather than remote communication between phases (e.g., oxygen spillover).