Raney-type catalysts were prepared by means of a two-step procedure: (i) mechanical alloying of the metals and (ii) alkaline aluminum leaching. Mechanical alloying is a novel alternative related to the synthesis of skeletal Ni catalysts. Catalysts characterization was performed by atomic absorption, X-ray diffraction, electron microscopy, and Mossbauer spectroscopies. Textural studies were also carried out. Binary Al-Ni and ternary Al-Ni-Fe alloys were produced by mechanical alloying from pure metallic powders; in particular, the intermetallic beta-(AlNi) phase was formed with a fine microstructure as a non-equilibrium phase; then, aluminum was selectively removed. After aluminum leaching the beta-(AlNi) phase was transformed into the more stable nickel fcc structure. The effect of iron addition to the Ni-Al catalysts depends on iron concentration and reduction temperature; both parameters determine catalysts composition and activity. This work reports physicochemical properties and benzene hydrogenation activity of these materials, compared with conventional catalysts obtained by melting and leaching.