A novel binuclear metallacyclic complex, [Cu(hfac)₂(bpmu)]₂, was isolated by reacting copper(II) hexafluoroacetylacetonate with the bpmu ligand. The crystal structure reveals the presence of dimetal units with the Cu(II) centers in a six-coordinate environment and bridged by the bpmu spacers. The crystal consists of a racemate with the two copper(II) ions of one dimer molecule carrying either a ΔΔ or ΛΛ configuration. The pyridyl-urea-based spacers are connected intramolecularly by the expected strong urea-based hydrogen bonds O=C(N–H)₂⋯O=C. The same type of H-bonds allows the molecular units of the same chirality to assemble forming supramolecular columns. This conformationally defined array and hydrogen-bonding network, together with the bulky properties of the fragment {Cu(hfac)₂}, were used as a pre-programmed supramolecular information for controlling the formation of discrete species.