We demonstrate the formation of hollow nickel germanide nanostructures of Ni-Ge core-shell nanoparticles by solid state reactions. The structural evolutions of nickel germanide hollow nanostructures have been investigated in real-time ultrahigh vacuum transmission electron microscopy (UHV-TEM). Annealed above 450 °C, the nonequilibrium interdiffusion of core and shell species occurred at the interface; thus, Ni germanide hollow nanostructures were formed by solid state reactions involving the Kirkendall effect. In addition, the different hollow nanostructures formed from different core diameters of Ni-Ge core-shell nanoparticles have been studied. Also, we propose the mechanism with effects of the size and annealing duration on the solid state reactions based on the Kirkendall effect.