Tellurium (Te) with a flower-like superstructure has been successfully synthesized through a low temperature biphasic solvothermal reaction utilizing diethyldithiocarbamato tellurium (IV) (TDEC) as Te source and 2,2′-dithiodibenzoic acid (DTBA) as a reducing agent. Characterizations by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM), energy dispersive X-ray spectroscopy (EDS), selected-area electron diffraction (SAED) show that the as-prepared product consists of well-aligned needle-like t-Te nanorods growing radically from the core. These nanorods have a diameter ranging from tens to hundreds of nanometers and a length of several micrometers, and the Raman spectra are greatly affected by their diameter. Fluorescence measurement reveals that the t-Te superstructures produce blue–violet emission.