Te nanorods mixed with Te nanoparticles were synthesized through a facile room temperature colloidal method in the presence of triethanolamine, acting as a surfactant. With quantities of triethanolamine≤3.0 mL, the nanorod-to-nanoparticle ratio increased as a function of the amount of triethanolamine while with 3.0 mL or more, only nanoparticles formed. Fourier transform infrared spectroscopy measurements confirmed that this surfactant-dependent growth was induced by the selective liganding of OH and C–C–O groups in triethanolamine. This selective liganding facilitated the selective assembly of Te nanorods through room-temperature electrophoretic deposition.