A series of NiCexAl (x = 0.1, 0.3, 0.5, 0.7 and 0.9) mixed metal oxides catalysts was synthesized through decomposing the corresponding layered double hydroxides (LDH) precursors, and then characterized by TG, XRD, N(2 )adsorption/desorption, XPS, H-2-TPR, H-2-TPD etc. techniques. The results showed that the introduction of Ce could efficiently restrict the agglomeration of Ni species. The generated Ni-Ce-O solid solution could create the oxygen vacancies and enhance the oxygen mobility which further improved the properties of active sites including Ni dispersion and surface area, and suppressed coke deposition. The Ni2+ species was reduced by Ce3+ under the reaction conditions to give the metallic Ni as active sites in catalyzing steam reforming of glycerol for the production of hydrogen. The best catalytic performance was obtained over the sample NiCe0.7Al which exhibited the better Ni dispersion and larger surface, and lower quantity of deposited coke by establishing the correlations. The reaction was more selective to hydrogen thanks to the enhancement of water gas shift reaction and suppression of CO methanation reaction. (C) 2020 Elsevier Ltd. All rights reserved.