Crystalline tubular magnesium oxide nanostructures were obtained through carbon-thermal evaporation of a MgO powder. Gallium oxide was added into the mixture of MgO and carbon. The reduction of gallium oxide by carbon resulted in gallium vapor at high temperatures. Condensed gallium droplets catalyzed the anisotropic growth of tubular MgO nanostructures in situ. The products were characterized by X-ray powder diffraction technique, scanning electron microscopy, and high-resolution microscopy. All the analyses indicated that the prepared tubular MgO nanostructures are, in fact, single crystals.