Rapidly quenched Zr2Ni amorphous and nanocrystalline ribbons were studied as electrocatalysts for hydrogen evolution in 6 M KOH. Linear polarization, potentiostatic hydrogen charge/discharge and EIS measurements at various potentials were carried out for the Zr alloys with different microstructure with the aim to extract information about the mechanism of hydrogen evolution and absorption and estimate the kinetic parameters of the hydrogen evolution reaction (HER). Though the melt-spun Zr62Ni33 alloys with varying microstructure do not show substantially different catalytic activity for HER, it could be clearly demonstrated that the nanocrystalline material reveals better catalytic performance than the entirely amorphous and nano-/amorphous alloys with the same chemical composition. It was found that all studied Zr-Ni alloys absorb hydrogen under the conditions of the hydrogen evolution experiments, as the amount of the absorbed hydrogen depends to a large degree on the alloys microstructure as well as on the applied potential during the HER experiment. The diffusion coefficient of hydrogen into the amorphous Zr62Ni33 alloy, as well as the thickness of the hydrided layer were found to be noticeably larger than those of the nanocrystalline alloy at the same conditions of hydrogen charging. Therefore the improved electrocatalytic properties of the nano crystalline alloy could only be explained by its favorable microstructure (e.g. higher density of defects) and weaker hydrogen absorption into the nanostructured material under the conditions of the HER. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.