The synthesis and single-crystal X-ray structure for tetraaquatetrakis(μ-2-propylvalerato)tetrakis(μ₄-salicylhydroximato)dysprosiumtetramanganesesodium dimethylformamide tetrasolvate, [DyMn₄Na(C₇H4NO₃)₄(C₈H₁₅O₂)₄(H₂O)₄]·4C₃H₇NO or DyNa(2-PV)₄[12-MC_{MnIII Nshi}-4](H₂O)₄·4DMF, 1, where MC is metallacrown, shi³⁻ is salicylhydroximate, 2-PV is 2-propylvalerate, and DMF is N,N-dimethylformamide, is reported. The slightly domed metallamacrocycle contains four ring Mn^III ions and four shi³⁻ ligands that generate an [Mn^III—N—O] repeat unit that recurs four times. The ring Mn^III ions are five-coordinate with a square-pyramidal shape. Furthermore, the metallacrown binds both a Dy^III ion and a Na⁺ ion in the central cavity. The central ions are located on opposite faces of the cavity with the Dy^III ion located on the convex side of the MC and the Na⁺ ion located on the concave side. Each central ion is eight-coordinate although they possess different geometries. The Dy^III ion has a square-antiprismatic shape, while the Na⁺ ion has an extremely distorted biaugmented trigonal–prismatic shape. The four 2-propylvalerate anions help to tether the Dy^III to the MC cavity by forming bridges between the Dy^III ion and each ring Mn^III ion. Moreover, the interstitial DMF molecules are hydrogen bonded to the water molecules that complete the coordination environment of the Na⁺ ion. The metallacrown framework (excluding the Dy^III and Na⁺ ions), the bridging 2-propylvalerate, and the interstitial DMF molecule experience whole-molecule disorder due to the rotational orientation of the metallamacrocycle. Additionally, the main moiety alkyl chain of the 2-propylvalerate is disordered over two additional orientations, and the main moiety interstitial DMF molecule is disordered over one additional orientation. The main moiety of the metallacrown framework refined to 0.9030 (14), while the minor B-moiety refined to 0.0971 (14). The main moiety alkyl chain of the 2-propylvalerate refined to 0.287 (3): 0.309 (3): 0.307 (3), and the minor B-moiety alkyl chain refined to 0.0971 (14). Lastly, the main moiety interstitial DMF refined to 0.549 (3): 0.354 (3), and the minor B-moiety DMF refined to 0.0971 (14).