The catalytic properties of Ni-25 at% Al (Ni25Al) nanoparticles fabricated by arc plasma evaporation toward methanol decomposition were studied at temperatures ranging from 513 to 753 K. The Ni25Al nanoparticles showed much higher activity than gas atomized Ni25Al powders. They showed a high degree of selectivity for methanol decomposition into H-2 and CO. Side reactions such as methanation and water-gas shift reaction were suppressed to a high temperature of 673 K, which is hardly achieved for common Ni catalysts. Detailed characterization of the Ni25Al nanoparticles showed that they were composed of Ni, Ni3Al, and Al2O3 phases with Ni and Al oxides on the surface of the Ni and Ni3Al phases. The Ni oxides were reduced to Ni phase by a hydrogen reduction prior to methanol decomposition, while the Al oxides remained unchanged. It is supposed that the Ni phase provided the active sites for methanol decomposition, and the Ni3Al and Al2O3 phases acted as supports for the Ni phase. Probably the Ni3Al and Al2O3 phases provided good resistance to agglomeration of the Ni phase during the reaction, which might contribute to maintain the high catalytic performance of the nanoparticles for methanol decomposition. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.