This article describes a rapid, solution-phase approach to the large-scale synthesis of faceted single-crystalline Se nanotubes, in the presence of cetyltrimethylammonium bromide. The products were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, laser Raman spectrography, differential scanning calorimetry analysis, and thermogravimetric analysis. The growth mechanism of the Se nanotubes was investigated by a series of experiments, and the rationality of the faceted morphology model for the Se nanotubes was demonstrated from the energetics and geometry. Furthermore, the electrochemical behavior of the Se nanotubes was studied by voltammetric techniques.