Triphenylenogermole, triphenylenodigermole, and trigermasumanene were prepared by repetitive lithiation of triphenylene followed by introduction of germanium functionalities. This is the first example of a trigermasumanene. Tin congeners were also synthesized and investigated. X-ray diffraction analysis of trisilasumanene 6, which does not have any substituents on the carbon atoms of the benzene rings, is also demonstrated. The optical properties of trigermasumanene and its derivatives were investigated by UV/Vis and fluorescence spectroscopy. Theoretical calculations were carried out to understand the properties of the thus-obtained triphenylenometallole derivatives.