The syntheses, crystal structures, and magnetochemical characterization are reported for three new mixed-valent Mn clusters [Mn8O3(OH)(OMe)(O2CPh)(7)(edte)(edteH(2))](O2CPh) (1), [Mn12O4(OH)(2)(edte)(4)Cl-6(H2O)(2)] (2), and [Mn20O8(OH)(4)(O2CMe)(6)(edte)(6)](CIO4)(2) (3) (edteH4 = (HOCH2CH2)(2)NCH2CH2N(CH2CH2OH)(2) = N,N,N',N'-tetrakis-(2-hyd roxyethyl) ethylenediami ne). The reaction of edteH(4) with Mn(O2CPh)(2), MnCl2, or Mn(O2CMe)(2) gives 1, 2, and 3, respectively, which all possess unprecedented core topologies. The core of 1 comprises two edge-sharing [Mn4O4] cubanes connected to an additional Mn ion by mu(3)-OH-ion and two alkoxide arms of edteH(2)(2-). The core of 2 consists of a [Mn-12(mu(4)-O)(4)](24+) unit with S4 symmetry. The core of 3 consists of six fused [Mn4O4) cubanes in a 3 x 2 arrangement and linked to three additional Mn atoms at both ends. Variable-temperature, solid-state dc and ac magnetization (M) studies were carried out on complexes 1-3 in the 5.0-300 K range. Fitting of the obtained M/N mu(B) vs H/T data by matrix diagonalization and including only axial zero-field splitting (ZFS) gave ground-state spin (S) and axial ZFS parameter (D) of S = 8, D = -0.30 cm(-1) for 1, S = 7, D = -0.16 cm(-1) for 2, and S = 8, D = -0.16 cm(-1) for 3. The combined work demonstrates that four hydroxyethyl arms on an ethylenediamine backbone can generate novel Mn structural types not accessible with other alcohol-based ligands.