We present the synthesis and structural characterization, assessed by various techniques (FTIR, TGA, UV-vis, elemental analysis, single-crystal X-ray diffraction for three compounds, magnetic susceptibility, and electrochemistry) of five manganese-containing Wells-Dawson sandwich-type (WDST) complexes. The dimanganese(II)-containing complex, [Na-2(H2O)(2)Mn-2(II)(As2W15O56)(2)](18-) (1), was obtained by reaction of MnCl2 with 1 equiv of [As2W15O56](12-) in acetate medium (pH 4.7). Oxidation of 1 by Na2S2O8 in aqueous solution led to the dimanganese(II) complex [Na-2(H2O)(2)Mn-2(III)(AS(2)W(15)O(56))(2)](16-) (2), while its trimanganese(II) homologue, [Na(H2O)(2)Mn-II(H2O)Mn-2(II)(AS(2)W(15)O(56))(2)](17-) (3), was obtained by addition of ca. 1 equiv of MnCl2 to a solution of 1 in 1 M NaCl. The trirnanganese(III) and tetramanganese(III) counterparts, [Mn-III(H2O)Mn-2(III)(As2W15O56)(2)](15-) (4) and [Mn-2(III)(H2O)(2)Mn-2(III)(As2W15O56)(2)](12-) (6), are, respectively, obtained by oxidation of aqueous solutions of 3 and [Mn-2(II)(H2O)(2)Mn-2(II)(As2W15O56)(2)](16-) (5) by Na2S2O8. Single-crystal X-ray analyses were carried out on 2, 3, and 4. BVS calculations and XPS confirmed that the oxidation state of Mn centers is +II for complexes 1, 3, and 5 and +III for 2, 4, and 6.A complete comparative electrochemical study was carried out on the six compounds cited above, and it was possible to observe the distinct redox steps Mn-IV/III and Mn-III/II. Magnetization measurements, as a function of temperature, confirm the presence of antiferromagnetic interactions between the Mn ions in these compounds in all cases with the exception of compound 2.