A biomolecule-assisted simple technique has been developed for the spontaneous ordering of the Bi2S3 nanorods into snowflakelike superstructures in high yield under microwave-hydrothermal conditions. In this method, glutathione (GSH) is used as both an assembling agent and a sulfur source. By controlling the molar ratio between bismuth nitrate and glutathione as well as the synthetic temperature, several kinds of Bi2S3 one-dimensional nanomaterials such as snowflakelike structures, nanowires constructed of particles, short nanorods, and fine and long nanowires have been controllably synthesized.