The metal oxides modified Ni/γ-Al2O3 catalysts for glycerol steam reforming were prepared by impregnation. Characterization results of fresh catalysts indicated that the molybdates modification abated the acidity and the stronger metal-support interaction of Ni/γ-Al2O3 catalysts, leading to a stable catalytic activity. Especially, NiMoLa-CaMg/γ-Al2O3 (NiMoLa/CMA) catalyst exhibited no deactivation along with glycerol complete conversion to stable gaseous products containing 69% H2, 20% CO and 10% CO2 during time-on-stream of 42 h. TPO of spent Ni/γ-Al2O3 catalysts modified by different components showed that the carbon deposit on acidic sites and NiAl2O4 species led to catalysts deactivation. A lower reforming temperature and a higher LHSV and glycerol content were helpful to the production of syngas from GSR over NiMoLa/CMA; the reverse conditions would improve the formation of H2.