Nanothread-based porous spongelike Ni3S2 nanostructures were synthesized directly on Ni foil by using a simple biomolecule-assisted method. By varying the experimental parameters, other novel Ni3S2 nanostructures could also be fabricated on the nickel substrate. The electrochemical hydrogen-storage behavior of these novel porous Ni3S2 nanostructures was investigated as an example of the potential properties of such porous materials. The thread-based porous spongelike Ni3S2 could electrochemically charge and discharge with the high capacity of 380 mAh g(-1) (corresponding to 1.4 wt % hydrogen in single-walled nanotubes (SWNT)). A novel two-charging-plateaux phenomenon was observed in the synthesized porous spongelike Ni3S2 nanostructures, suggesting two independent steps in the charging process. We have demonstrated that the morphology of the synthesized Ni3S2 nanostructures had a noticeable influence on their electrochemical hydrogen-storage capacity. This is probably due to the size and density of the pores as well as the microcosmic morphology of different nickel sulfide nanostructures. These novel porous Ni3S2 nanostructures should find wide applications in hydrogen storage, high-energy batteries, luminescence, and catalytic fields. This facile, environmentally benign, and solution-phase biomolecule-assisted method can be potentially extended to the preparation of other metal sulfide nanostructures on metal substrates, such as Cu, Fe, Sn, and Pb foils.