Ni catalysts based on ternary mixed oxides, NiMAl (M = Mg, Ca, Zn) and NiMgN (N = La, Ce) were prepared by the coprecipitation method and characterized by N-2-sorption measurements, TGA, XRF, XRD, H-2-TPR and TEM. NiMAl(M = Mg, Ca, Zn) catalyst precursors exhibited a layered double hydroxide (LDH) structure, not observed in NiMgN (N = La, Ce) samples. NiMgAl mixed oxide exhibited well-stabilized nickel species needing high temperatures to be reduced (around 1100 K). The extent of Ni2+ reduction in the mixed oxides was improved with the replacement of Mg by Ca and Zn or Al by La and Ce. Catalysts were very active and selective in ethanol steam reforming although NiMgN (N = La, Ce) samples deactivate faster than NiMAl (M = Mg, Ca, Zn) having smaller Ni crystallites. In particular, the presence of Ca produced an important dispersing effect over the Ni species, favouring hydrogen production while keeping moderate coke formation. In the case of the reduced NiCaAl mixed oxide H-2 selectivity values above 87 mol % were reached. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.