Amorphous Zr64Ni36 and Zr48Ni27Al25 alloys have been characterized by physico-chemical, structural and electrochemical techniques in view of their possible application as electrocatalytic materials for hydrogen evolution reaction. Phase transformations of the amorphous materials have been observed by X-ray diffraction and differential scanning calorimetry. The electrocatalytic efficiency has been evaluated on the basis of electrochemical data obtained from cathodic polarization curves carried out in 1 M KOH at 25 degrees C. The results have been compared to those obtained on polycrystalline nickel. The overall experimental data indicate that interesting electrocatalytic performances are obtained with samples chemically pre-treated in HF solutions. In the case of Zr48Ni27Al25 alloy a leaching pretreatment was also tried with the purpose of obtaining a highly micro-porous structure as a consequence of Al elimination.