Two nickel-aluminum hydrotalcite type precursors were synthesized with molar ratio Ni/Al = 3, using hydroxyl and carbonate as compensation anions. These precursors were intercalated by 30% (theoretical) decavanadate anion. The catalysts were obtained after calcination at 550 degrees C and their performance was evaluated in propane oxidative dehydrogenation at 400 degrees C using space velocities of 100, 150, 200 and 400 ml g(-1) min(-1) under conditions of oxygen deficiency and oxygen excess. Catalysts derived from nickel-aluminum-hydroxyl precursors attained an excellent performance under oxygen deficiency conditions promoting high propene selectivity and conversion. Under oxygen excess conditions the catalyst was more active but its selectivity was lower. Vanadium-containing catalysts showed improved selectivity under this operation condition. The formation of the hydrotalcite phase in precursors and mixed oxides in the catalysts was evidenced by X-ray diffraction (XRD). Analyses of textural and reduction properties were carried-out with nitrogen adsorption and temperature programmed reduction techniques respectively. Structural studies were performed by X-ray absorption spectroscopy for materials that showed best performance in the oxidative dehydrogenation reaction. (c) 2012 Elsevier B.V. All rights reserved.