Biomacromolecules such as proteins, although extremely complex in microstructure, can crystallize into macro-sized crystals after self-adjusting their shapes, based on which the structure of biology is built. Inorganic nanowires/nanoribbons with a similar one-dimensional topology but much simpler structures can hardly be as flexible as macromolecules when constructing superlattice structures because of their inherent rigidity. Here we report the synthesis of crystalline indium sulfide nanoribbon-based nanocoils that are formed by spontaneous self-coiling of ultrathin nanoribbons. The nano-structures are flexible and appear as relatively random coils because of their ultrathin ribbon structures (similar to 0.9 nm in thickness) with high aspect ratios. Moreover, the nanocoils can self-adjust their shapes and assemble into two-dimensional superlattices and three-dimensional supercrystals in solution. The ultrathin nanocoils are expected to bring new insights into the use of flexible nanocrystals as building blocks for constructing superstructures.