The formation of amorphous and quasicrystalline phases in the Ti45Zr38Ni17 system both directly by mechanical alloying and after subsequent annealing was studied. The presence of amorphous, icosahedral quasicrystalline and the Ti2Ni-type with a fcc structure phases together with the initial metallic components was found in as-milled samples by X-ray diffraction. An increase of the milling time results in an increase of the amorphous phase content. Icosahedral quasicrystalline phases of Ti–Ni–Zr system were produced by mechanical alloying and subsequent annealing. Differential scanning calorimetry studies up to 520°C showed an extended exothermal effect starting from 300°C, which corresponds to the crystallization of the as-milled samples. The shape and size of the particles of the alloys were investigated by scanning electron microscopy and argon adsorption. The Specific area surface of the as-milled sample was rather small, in agreement with scanning electron microscopy data. The kinetics of the hydrogenation of the amorphous alloy Ti45Zr38Ni17 at different temperatures was studied.