The NixMg1-xAl2O4, NiCr2O4, and MgCr2O4 spinels have been synthesized, characterized with the XRD and XPS methods, and tested in the oxidative dehydrogenation of propane. The crystallochemical model of solid surfaces, CMSS, has been used to calculate the oxygen cation＇s bond energies in the spinels. For the NiMgAl spinels the activity and selectivity to propene increase with the increase in the Ni content. The Ni ions surrounded by oxygen in the spinel structure are proposed as active centers for oxidative dehydrogenation to propene. The NiCr spinel is more active but less selective than the NiMgAl spinels; the difference in catalytic behavior has been ascribed to different coordination of Ni ions in the two groups of the spinels and to the lower oxygen cation＇s bond energy in the NiCr spinel.