For the first time, hexanuclear complexes with general chemical formula [Ln(6)O(OH)(8)(NO3)(6)(H2O)(n)](2+) with n = 12 for Ln = Sm-Lu and Y and n = 14 for Ln = Pr and Nd were stabilized as nanoaggregates in ethylene glycol (EG). These unprecedented nano-aggregates were structurally characterized by Y-89 and H-1 NMR spectroscopy, UV-vis absorption and luminescence spectroscopies, electrospray ionization mass spectrometry, diffusion ordered spectroscopy, transmission electron microscopy, and dynamic light scattering. These nanoaggregates present a 200 nm mean solvodynamic diameter. In these nanoaggregates, hexanuclear complexes are isolated and solvated by EG molecules. The replacement of ethylene glycol by 2-hydroxybenzyl alcohol provides new nanoaggregates that present an antenna effect toward lanthanide ions. This results in a significant enhancement of the luminescence properties of the aggregates and demonstrates the suitability of the strategy for obtaining highly tunable luminescent solutions.