Ni-based catalysts doped with copper additives were studied on their role in ethanol steam reforming reaction. The effects of Cu content, support species involving Al 2O 3-SiO 2, Al 2O 3-MgO, Al 2O 3-ZnO, and Al 2O 3-La 2O 3, on the catalytic performance were studied. Characterizations by TPR, XRD, NH 3-TPD, XPS, and TGA indicated that catalysts 30Ni5Cu/Al 2O 3-MgO and 30Ni5Cu/Al 2O 3-ZnO have much higher H 2 selectivity than 30Ni5Cu/Al 2O 3-SiO 2, as well as good coke resistance. H 2 selectivity for 30Ni5Cu/Al 2O 3-MgO catalyst was 73.3% at 450 °C and increased to 94.0% at 600 °C, whereas for 30Ni5Cu/Al 2O 3-ZnO catalyst, the H 2 selectivity was 63.6% at 450 °C and 95.2% at 600 °C. These Al 2O 3-MgO and Al 2O 3-ZnO supported Ni-Cu bimetallic catalysts may have important applications in the production of hydrogen by ethanol steam reforming reactions.