The cluster compounds [Nb6I8Py6] and [Nb6I8Py6]I·9Py, both with octahedral Nb6 metal atom cores were obtained from the reaction of [Nb6I11] with pyridine (Py). Both compounds are rare examples of iodide supported hexanuclear cluster compounds, which are obtained through solvent-based chemical reactions. The Nb6 cluster core is surrounded by µ3-bridging iodido and apical-bonded pyridine ligands. [Nb6I8Py6] contains 22 cluster-based electrons (CBE’s), whereas [Nb6I8Py6]I·9Py is the oxidized version with 21 CBE’s. The oxidation happens just by lowering the temperature from room temperature to -20 °C of the same starting materials as used for [Nb6I8Py6]. The structures of the two cluster compounds were determined by single-crystal X-ray diffraction.