The self-assembly of the first pentanuclear helicate was predicted on the structural basis obtained for linear and tetranuclear parent supramolecular compounds. Accordingly, the designed ternary supramolecular system requires appropriate polytopic organic receptors, which were successfully synthesized. Indeed, the formation of pentanuclear complexes was experimentally evidenced with NMR and ESMS spectra that perfectly reflect the expected pattern. The structural features in the europium pentanuclear complex are highlighted with semiempirical molecular modeling. The present work validates the combinatorial approach leading to the thermodynamically driven formation of tower-like pentanuclear edifices.