The nanocrystalline Mg2Ni-type electrode alloys with nominal compositions of Mg20Ni10-xCux (x = 0, 1, 2, 3,4) were synthesized by the melt spinning technique. The microstructures of the as-cast and spun alloys were characterized by XRD, SEM and HRTEM. The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system. The results show that all the as-spun alloys hold typical nanocrystalline structure instead of an amorphous phase. The melt spinning does not modify the major phase Mg2Ni, but it leads to the formation of crystal defects such as stacking faults, dislocations, sub-grain boundary and twin-grain boundary. The melt spinning significantly improves the electrochemical hydrogen storage capacity of the alloys, whereas it slightly impairs the electrochemical cycle stability of the alloys. The substitution of Cu for Ni significantly ameliorates the electrochemical hydrogen storage performances of the alloys, involving both the electrochemical hydrogen storage capacity and the electrochemical charging and discharging stability. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.