Composites of Ti1.4V0.6Ni alloy and various amounts of multiwalled carbon nanotubes (MWNTs) have been synthesized by high energy mechanical ball-milling method. The composites mainly contain icosahedral quasicrystal and TiNi-type phases. In contrast to Ti1.4V0.6Ni, all milled composites have excellent activation properties activated at the first charge/discharge cycle, together with excellent rate discharge abilities. The composites are able to deliver outstanding maximum discharge capacities of 295.5 mAh g(-1) enhanced by 68.2 mAh g(-1) in comparison to Ti1.4V0.6Ni alloy, and good cycling stabilities with capacity retention of more than 40% after 100 charge/discharge cycles higher than Ti1.4V0.6Ni alloy. Experimental and theoretical investigations suggest that the unusual electrochemical performance of this composite is depended on the copacetic electrocatalytic activity of MWNTs addition and the enhancement of hydrogen diffusion progress. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.