The structure of the title compound, Mn(II)[Fe(III)(CN)(6)](2/3)·5H(2)O, features a face-centered cubic -Mn-NC-Fe- framework with both Mn and Fe having site symmetry mm. Since one-third of the [Fe(CN)(6)](3-) units are missing for a given formula in order to maintain charge neutrality, each Mn atom around such a vacancy is coordinated not only by the N atoms of the CN groups but also by the O atoms of the ligand water mol-ecules. In addition to ligand water mol-ecules, two types of non-coordinated water mol-ecules, so-called zeolitic water mol-ecules, exist in the inter-stitial sites of the -Mn-NC-Fe- framework. The positions of the O atoms of the zeolitic water mol-ecules are fixed by the linkage via hydrogen bonds between ligand water and zeolitic water mol-ecules. The structure is related to a recently reported rubidium manganese hexa-cyano-ferrate. Site occupancy factors for Fe, C, N are 0.67; for two O atoms the value is 0.83 and for one O atom is 0.17.