Single-crystalline Bi2S3 and Sb2S3 nanorods have been successfully synthesized by the microwave-assisted ionic liquid method. The starting reagents were Bi2O3 or Sb2O3, HCl, Na2S2O3, and ethylene glycol (EG) or ethanolamine, and the ionic liquid used was 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), Our experiments showed that the ionic liquid played an important role in the morphology of M2S3 (M = Bi, Sb). Single-crystalline Bi2S3 nanorods could be prepared in the presence of [BMIM][BF4]. However, urchinlike Bi2S3 structures consisting of nanorods were formed without using [BMIM][BF4]-Single-crystalline Sb2S3 nanorods were obtained in the presence of [BMIM][BF4]. However, single-crystalline Sb2S3 nanosheets could be prepared in the absence of [BMIM][BF4]. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and electron diffraction (ED).