The steam reforming of glycerol over supported nickel catalysts is a promising and cost-effective method for producing hydrogen. The activity of nickel catalysts supported on gamma-Al2O3 is low, primarily due to the formation of inactive nickel species during high temperature calcination in air. In order to address this problem, a Ni/gamma-Al2O3 catalyst was prepared by calcination at 700 degrees C in a nitrous oxide (N2O) environment. The N2O calcined catalyst showed an enhanced activity for the steam reforming of glycerol. A variety of characterization techniques (XRD, TPR, XPS and H-2 Chemisorption) confirmed that the high temperature N2O calcination resulted in a significant decrease in the levels of nickel aluminate. The N2O calcination also led to an enhancement in the amount of NiO as well as nickel ions present on the surface of the catalyst. Interestingly, compared to an air calcined catalyst, the N2O calcined catalyst contained larger nickel particles after reduction but the N2O calcined catalyst had a much larger nickel surface area and dispersion, which resulted in higher glycerol conversion and hydrogen yield. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.