The structure of melt-spun and crystallized Mg-10%Ni and Mg-10%Ni-5%La alloys is studied using HRTEM, coupled with ED and EELS techniques, for specimens subjected to hydrogenation and dehydrogenation. The presence of nano-sized (5-10nm) Mg2Ni grains dispersed in the matrix of Mg nano-grains is observed before hydrogenation. This structure is almost preserved after hydrogenation and dehydrogenation at 300°C. In the hydrogenated specimen, nanoboundaries lying between MgH2 and Mg2NiH4 nano-grains are observed. They appear to provide main routes for the hydrogen transport in these nanostructured materials.