A series of Ni2+-Fe2+-Al3+ hydrotalcite (HT) catalysts with varying compositions have been prepared by coprecipitation from Fe2+. The structure and properties of the catalysts were carefully characterized by various methods such as XRD, EXAFS, TGA, TPR, N-2 adsorption/ desorption, XPS and H-2 chemisorption. It was shown that pure HT structures can only be prepared at low Fe2+ concentrations, while mixed oxide phases with spinet structure will form simultaneously at high Fe2+ concentrations. Pure HT structures are very important for small particle size, narrow size distribution and large surface area of the resulting catalysts. XPS study demonstrated Fe enrichment on the catalyst surfaces, which might have partly contributed to the low hydrogen chemisorption capacity for the Fe-containing catalysts. (c) 2008 Elsevier B.V. All rights reserved.