A general hydrothermal method was developed for the preparation of well-crystallized V2VI3 (V = Sb and Bi; VI = S, Se, and Te) thermoelectric nanomaterials directly from the corresponding elemental powders. X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) techniques were used to characterize the products and investigate the possible reaction mechanism.