Intermetallic Ni3Al–based alloys (doped with zirconium and boron) represent a group of advanced materials with potential outstanding physical and chemical properties (such as high catalytic activity and structural stability in corrosive environments) that make them a considerable candidate for many high-tech applications. In this paper, the catalytic activity of fully dense Ni3Al-based thin foils (as thin as 50 m) possessing structures with micrometer or nanometer grain sizes is discussed. The examined material, without any additional catalytic coating, was successfully produced from as-cast coarse-grained sheets by heavy cold rolling and recrystallisation with an appropriately chosen set of parameters. The examination focuses on methanol and methanol/water mixture decomposition into H2 and CO at temperatures up to 530OC in a quartz reactor. Except for these products, a small amount (below 1%) of CO2 and dimethyl ether was observed. The catalyzed reaction began effectively at about 400OC, with a methanol conversion of about 90% or higher.