The catalytic activity of oxidation-reduction pre-treated Ni3Al powder for methane steam reforming was examined. The oxidation-reduction pre-treatment consisted of two steps: oxidation in air at various temperatures from 973 to 1373 K, and then followed by reduction in H2 at 873 K. It was found that the oxidation-reduction treatments significantly reduced the onset temperature of activity, i.e., improved the activity of Ni3Al powder at low temperatures. The characterization of Ni3Al surface showed that an outer surface layer of fine NiO particles were formed on the surface of Ni3Al after oxidation. These NiO particles were reduced to metallic Ni by the subsequent reduction treatment, resulting in the high activity for methane steam reforming. These results indicate that the Ni3Al can form highly active surface structure with oxidation-reduction treatment, having excellent heat resistance.