The structural and electrocatalytic properties of metastable Ni-Mo alloys have been investigated for the hydrogen evolution reaction in alkaline solutions. Amorphous and nanocrystalline phases have been prepared by mechanically alloying the elemental components under various milling conditions. Fcc nanocrystals are formed when the Mo concentration is smaller than 30 at. %. The nanocrystalline state becomes unstable with respect to the amorphous phase when the Mo content in the solid solution exceeds 30 at. %. The electroactive phase for the hydrogen evolution reaction in alkaline solutions is the nanocrystalline supersaturated solid solution. The presence of oxygen during the milling process improves the properties of the alloys.