In this paper the catalytic steam reforming of glycerol to H2 has been evaluated in the presence of Mo/γ-Al2O3 and Mo/γ-Al2O3-MgO in a fixed-bed microreactor at 700 °C. Physiochemical properties of the Mo catalysts were explored by various analytical techniques such as N2 adsorption-desorption (BET), X-ray diffraction (XRD), X-ray fluorescence spectrum (XRF), Temperature-programmed reduction (TPR) and Transmission Electron Microscopy (TEM). Mo/γ-Al2O3-MgO catalysts show promising results with higher glycerol conversion and higher H2 selectivity as compared to Mo/γ-Al2O3 catalysts. The Mo was found to be uniformly distributed on the surface of γ-Al2O3-MgO support and addition of MgO contents into γ-Al2O3 improves the dispersion of Mo on the surface of the support. © (2014) Trans Tech Publications, Switzerland.