Abstract The effect of vanadium doping on the kinetics and thermodynamics of hydrogenation–dehydrogenation process of Mg 2 Ni have been investigated. Two samples, Mg 2 Ni-5 wt.% V and Mg 2 Ni-10 wt.% vanadium were prepared by ball milling process. The hydrogenation–dehydrogenation kinetics along with pressure–composition isotherm (PCT) of vanadium doped and pure-Mg 2 Ni samples were studied. The sample Mg 2 Ni-5 wt.% V has shown improved hydrogenation–dehydrogenation kinetics with extended plateau region as compared to pure-Mg 2 Ni under similar conditions. Marginal changes in the enthalpies of hydrogenation–dehydrogenation have been observed on vanadium addition. The improved properties could be beneficial for the viable commercial applications of Mg 2 Ni as a negative electrode of metal-hydride batteries and as a material for hydrogen storage.