H-2 production from ethanol steam reforming (H2O/EtOH=3) in concentrated conditions (14% of ethanol) was studied over NiXMg2AlOY catalysts derived from the hydrotalcite-like precursors. Various physicochemical techniques were employed to characterize the catalysts, such as XRD, XPS, H-2-TPR, in situ XRD, O-2-TPO and Raman. Different parameters were carefully analyzed, including reaction temperature, in situ activation in H-2, Ni content and their influence on the efficiency of the catalysts was studied. It is found that well tuning the NiXMg2AlOY catalysts and their pre-treatment in H-2 lead to new benefits in both material properties and catalytic performances. The co-precipitation method allows obtaining uniform NiXMg2AlOY mixed oxides possessing very active Ni species in small nanoparticles (3-4 nm) of mixed oxides, which are more difficult to reduce compared to bulk NiO due to the strong interactions between Ni cations and Mg and/or Al cations. NiXMg2AlOY mixed oxides are shown as active and efficient catalysts for H-2 production from ethanol in the presence of water. In diluted conditions (3% of ethanol) the catalysts enable to totally convert ethanol at 450 degrees C and to provide a CO-free H-2 production of 3.0 mol mol(EtOH)(-1). A higher and competitive H-2 yield of 5.0 mol mol(Eto)(-1) can be achieved at 650 degrees C. The catalysts show good catalytic stability with the time on stream even though solid carbon is formed. (C) 2014 Elsevier B.V. All rights reserved.