Lanthanide-cored self-assembled complexes consisting of cores (Tb3+ and Eu3+) and surrounding aromatic dendritic subunits were prepared and characterized. Luminescence experiments provided experimental evidence supporting the proposed self-assembled structure. This new class of complexes exhibited enhanced luminescence activity as the dendritic subunit size increased. This enhancement was attributed to both the sensitization of the core cation and the site exclusion that keeps the Ln(3+) cores apart from one another leading to a decrease in the rate of self quenching.