Sequential reaction of the multisite coordination ligand (LH3) with Cu(OAc)(2)center dot H2O, followed by the addition of a rare-earth(III) nitrate salt in the presence of triethylamine, afforded a series of heterometallic heptanuclear complexes containing a [Cu(5)Ln(2)] core (Ln = Y(1), Lu(2), Dy(3), Ho(4), Er(5), and Yb(6)). Single-crystal X-ray crystallography reveals that all the complexes are dicationic species that crystallize with two nitrate anions to compensate the charge. The heptanuclear aggregates in 1-6 are centrosymmetrical complexes, with a hexagonal-like arrangement of six peripheral metal ions (two rare-earth and four copper) around a central Cu(II) situated on a crystallographic inversion center. An all-oxygen environment is found to be present around the rare-earth metal ions, which adopt a distorted square-antiprismatic geometry. Three different Cu(II) sites are present in the heptanuclear complexes: two possess a distorted octahedral coordination sphere while the remaining one displays a distorted square-pyramidal geometry. Detailed static and dynamic magnetic properties of all the complexes have been studied and revealed the single-molecule magnet behavior of the Dy(III) and Ho(III) derivatives.