The skeletal Pd catalysts were prepared from Pd-Zr alloys which possess amorphous or crystalline state. The hydrogenation of 1-octene to octane over skeletal Pd catalysts proceeded efficiently while Pd-Zr alloy was inactive. The skeletal Pd prepared from amorphous alloy showed higher catalytic activities despite the smaller surface area compared to that prepared from the corresponding crystalline alloy. These catalytic activities were attributed to the number of surface-exposed Pd of skeletal Pd which was strongly affected by the atomic arrangement of the precursor. Moreover, we investigated the effect of Ni addition to the P-Zr alloy as the third metal. Skeletal Pd with 16 at% Ni showed an excellent selectivity while keeping as high catalytic activity as skeletal Pd. (C) 2015 Elsevier B.V. All rights reserved.