Two mixed-valence Mn(II,IV) complexes, [Mn II 4 Mn IV 3 (teaH) 3 (tea)(thmeH) 3 (thme)](ClO 4 ) 2 ·3MeCN ( 1 ) and [Mn II 2 Mn IV 2 (edteH) 2 (peolH) 2 ]·4MeOH ( 2 ), where H 4 edte = N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine, teaH 3 = tris(2-hydroxyethyl)amine, H 4 peol = pentaerythritol, and H 3 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 II and 3Mn IV for 1 , 2Mn II and 2Mn IV ions for 2 . Complex 1 crystallizes in the rhombohedral space group R 3c, while 2 crystallizes in the monoclinic space group P 2 1 /c. Complex 1 consists of a near-planar Mn 7 unit that comprises a Mn 6 hexagon of alternating Mn II and Mn IV ions surrounding a central Mn II ion. The remaining coordinated sites are occupied by eight different deprotonation degrees of H 3 tea or H 3 thme. The tetranuclear cluster of 2 consists of a fused defective dicubane Mn 4 O 6 core, and the four Mn ions are coordinated by oxygens from edteH 3− and peolH 3− into an unusual butterfly-like [Mn II 2 Mn IV 2 ] 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.