New binuclear complex 1,2-bis[2-(4,4,4-trifluoro-1-hydroxy-3-oxobut-1-enyl)phenoxy]ethanedi(dimethylformamide)dicopper(II) is synthesized, and its structure is studied by X-ray diffraction (XRD) (CIF file CCDC no. 2179252). A crystal of the complex is formed by centrosymmetric Cu2L2(DMF)2 molecules in which the coordination environment of each metallocenter is a distorted square pyramid, and the whole molecule is a metallomacrocycle containing the calixarene-like cavity. Its size is determined the distance between the Cu…Cu metallocenters (7.699 Å) and the distance between the planes of the opposite phenyl radicals in the cis position (8.200–8.323 Å). The cavity is a parallelogram. The carcass-type binuclear structure is formed due to an increase in the denticity of the ligand via the formation of the bis(triketone)-like structure that weakens the donor character of both functional groups of the β-diketone fragment.