Mg-10 wt% Ni alloys containing up to 1 wt% Nb were fabricated by a casting technique, followed by ball-milling with 5 wt% multi-walled carbon nanotubes. Further mechanical alloying with 1.5, 3, and 5 at % Nb was applied to a cast Mg-10 wt% Ni-370 ppm Nb alloy to investigate the catalytic role of Nb in hydrogen dissociation. The microstructure and distribution of Nb and Mg(2)Ni in the alloys were characterised by SEM. The absorption and desorption kinetics of the samples were measured by Sieverts' apparatus at various temperatures. The results show that addition of Nb during casting accelerates the hydrogen diffusion compared to the cast binary Mg-10 wt% Ni alloy. Moreover, ball-milling of the alloy with metallic niobium leads to the formation of BCC phase of Mg-Nb solid solution, which significantly improves the hydrogenation properties of the alloy. DSC results show that mechanical alloying of Mg-10 wt%Ni-370 ppm Nb with Nb in excess of 1.5 wt% decreases the desorption temperature by approximately 100 C compared to the ball-milled cast alloy. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.