Hydrogen was produced by methanol decomposition over cold-rolled foils of intermetallic compound Ni3Al which is known as an excellent high-temperature structural material. We found high catalytic activity and selectivity for methanol decomposition in flat cold-rolled Ni3Al foils. The catalytic activity was enhanced above 713 K by the spontaneous formation of fine Ni particles dispersed on carbon nanofibers during the reaction, resulting in high catalytic performance. The results demonstrate that the Ni3Al foils can be used both as catalyst precursors and as structural materials of microreactors for hydrogen production.