The effect of vanadium doping on the kinetics and thermodynamics of hydrogenation–dehydrogenation process of Mg2Ni have been investigated. Two samples, Mg2Ni-5 wt.% V and Mg2Ni-10 wt.% vanadium were prepared by ball milling process. The hydrogenation–dehydrogenation kinetics along with pressure–composition isotherm (PCT) of vanadium doped and pure-Mg2Ni samples were studied. The sample Mg2Ni-5 wt.% V has shown improved hydrogenation–dehydrogenation kinetics with extended plateau region as compared to pure-Mg2Ni 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 Mg2Ni as a negative electrode of metal-hydride batteries and as a material for hydrogen storage.