Ln–Mg–Al mixed oxide catalysts (Ln = Ce, Sm, Dy, Yb) were prepared from layered double hydroxide precursors, characterized using XRD, N₂ adsorption, TG-DTG, EDX, H₂-TPR and CO₂-TPD techniques and tested in the oxidative dehydrogenation of propane in the temperature range 450–600 °C. For all the catalysts the conversion increases with increasing the reaction temperature while the propene selectivity decreases to the benefit of carbon oxides for Ce-based system and of cracking products for the others. The best yields in propene were obtained with Dy- and Sm–Mg–Al–O catalysts. No correlation between the reducibility of the rare-earth cation and the catalytic performances was observed. A linear correlation between the catalyst basicity and the propene selectivity was evidenced.