While the pure Au16 cluster tends to exist in a 3D cage shape, the doubly doped W2@Au16 is found to prefer a tubular form containing three fve-membered Au rings stabilized by the W2 dimer vertically placed inside a tube-like Au16 framework. Formation of self-assembled nanotubes containing fve-membered Au rings from the tube-like W2@Au16 cluster is also feasible, and such a tubular structure constitutes an ideal building block for generating gold-assembled nanotubes, providing us with a useful approach for designing some novel tailor-made materials with interesting optoelectronic properties. Methods Density functional theory (DFT) calculations using the TPSS functional and the cc-pVDZ-PP basis set are employed to determine some noticeable efects of the doping of the W2 dimer on the structure, stability, and optical properties of pure Au16 gold clusters.