<p>Two mixed-valence Mn(II,IV) complexes, [Mn<sup>II</sup><sub>4</sub>Mn<sup>IV</sup><sub>3</sub>(teaH)<sub>3</sub>(tea)(thmeH)<sub>3</sub>(thme)](ClO<sub>4</sub>)<sub>2</sub>·3MeCN (<b>1</b>) and [Mn<sup>II</sup><sub>2</sub>Mn<sup>IV</sup><sub>2</sub>(edteH)<sub>2</sub>(peolH)<sub>2</sub>]·4MeOH (<b>2</b>), where H<sub>4</sub>edte = N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine, teaH<sub>3</sub> = tris(2-hydroxyethyl)amine, H<sub>4</sub>peol = pentaerythritol, and H<sub>3</sub>thme = 1,1,1-tris(hydroxymethyl)ethane, were prepared from the corresponding manganese salts and mixed ligands with polyalcohols. The two clusters consist of a trapped-valence polynuclear core comprising 4Mn<sup>II</sup> and 3Mn<sup>IV</sup> for <b>1</b>, 2Mn<sup>II</sup> and 2Mn<sup>IV</sup> ions for <b>2</b>. Complex <b>1</b> crystallizes in the rhombohedral space group <i>R</i>3c, while <b>2</b> crystallizes in the monoclinic space group <i>P</i>2<sub>1</sub>/c. Complex <b>1</b> consists of a near-planar Mn<sub>7</sub> unit that comprises a Mn<sub>6</sub> hexagon of alternating Mn<sup>II</sup> and Mn<sup>IV</sup> ions surrounding a central Mn<sup>II</sup> ion. The remaining coordinated sites are occupied by eight different deprotonation degrees of H<sub>3</sub>tea or H<sub>3</sub>thme. The tetranuclear cluster of <b>2</b> consists of a fused defective dicubane Mn<sub>4</sub>O<sub>6</sub> core, and the four Mn ions are coordinated by oxygens from edteH<sup>3−</sup> and peolH<sup>3−</sup> into an unusual butterfly-like [Mn<sup>II</sup><sub>2</sub>Mn<sup>IV</sup><sub>2</sub>] topology. The two clusters are also characterized by mass spectra and X-ray photoelectron spectroscopy. Direct current magnetization studies reveal ferromagnetic interactions within both Mn clusters.</p
