The freestanding Sb2S3 films were easily synthesized at the interface of water and toluene at room temperature, where Na2S and (C2H5OCS2)(3)Sb (xanthate, O-ethyldithiocarbonate) acted as sulfur and antimony source, respectively. After 3 h of aging, the Sb2S3 films with a flat surface toward organic side and rough surface toward aqueous side were assembled by sheaflike Sb2S3 nanowires. The Sb2S3 nanorings formed by end-to-end connection of the bundled nanowires appeared in the water layer when the reaction time reached 24 h. The Sb2S3 nanorings showed higher photocatalytic activity for methyl orange degradation under visible light than the Sb2S3 films owing to broader spectrum response and better aqueous dispersion.