Rapid quenching technique can be used for designing new amorphous and quasicrystalline Zr-based materials. Zr-Cu-Ni-Al alloys are of great interest for hydrogen storage. Hydrogen charging of amorphous as well as quasicrystalline Zr69.5Cu12Ni11Al 7.5 was performed electrochemically in a 2:1 glycerin-phosphoric acid electrolyte. Absorption kinetics and storage capacity were found to be far better for the partially quasicrystalline than for the amorphous material. Only partial desorption of hydrogen was observed by TDA at about 500°C of glassy or quasicrystalline Zr-Cu-Ni-Al. Since hydrogen desorption seems to be hindered by a surface barrier, the hydrogen remains in the Zr-based alloys, thus influencing their thermal stability. These apparent limits to hydrogen desorption were studied by DSC, TDA and microstructure investigations. At low hydrogen concentration (H/M ≤ 0-15) the absorption of hydrogen causes a significant increase in the thermal stability of the amorphous phase; at high hydrogen concentrations (H/M ≥ 0.9) the formation of ε - ZrH 2-x and δ - ZrH2 was revealed. It is concluded that hydrogen can be used to control the thermal stability and crystallization process of Zr-based amorphous alloys. The micromechanism of the decomposition during annealing of hydrogenated Zr-based metallic glasses or quasicrystals are discussed in detail.