Skeletal Ni catalysts were prepared from an amorphous Ni40Zr60 alloy (a-NiZr) by heating at various temperatures under vacuum, followed by the selective extraction of Zr moieties by an HF treatment. Each sample was characterized by various spectroscopic methods, and the catalytic performance was tested in the hydrogenation of 1-octene. The differences in preparation temperatures of a-NiZr strongly affected the catalytic performance of the obtained catalysts, whereby those prepared from heated a-NiZr in the pre-crystallization state exhibited higher catalytic activity. Especially, moderate thermal treatment of a-NiZr at a temperature slightly lower than that for its crystallization, that is, ∼573 K, resulted in a significant enhancement of the catalytic activity. Such prepared skeletal Ni catalyst can also be used efficiently for hydrogen generation from aqueous hydrazine.