Herein, we report a method for the preparation of the first odd homometallic and heterovalent nine-centered Tc wheel, [Tc 9 (μ-O) 9 Cl 6 (OOCCl 3 ) 15 ]. The synthesized compound represents the pioneering instance of such clusters among d 4 elements and is the fourth instance observed across all metals. The ring was synthesized by a solvothermal method in a solution of technetium acid in trichloroacetic anhydride. By single-crystal X-ray diffraction (XRD), powder XRD, and FTIR, the crystal structure was established. By UV−vis spectroscopy, thermogravimetric analysis, and density functional theory calculations, the optical, thermal, and some chemical properties were studied. The molar extinction coefficients in 16 solvents were determined. The heating of the complex in trichloroacetic anhydride leads to the formation of carbonyl compounds.