Eu 3+ -, Tb 3+ - and Er 3+ -cored dendrimer complexes were prepared by self-assembly of three fluorinated dendrons, each with a carboxylate anion focal point, around the lanthanide ion. Energy transfer from the peripheral fluorinated phenyl moieties of the dendrons to the lanthanide cation was evidenced spectroscopically for Eu 3+ - and Tb 3+ -cored dendrimer complexes in solution. The excitation of perfluorinated aromatic groups was found to decay with ca. 0.7ns and a longer decay time 10–13ns was related to the coordination at the Ln 3+ focal point. Luminescence from the lanthanide core decays with lifetime in the range 1–1.5ms over a wide concentration range (μM–mM), similar to the luminescence decay time of the corresponding acetate ion complexes in D 2 O. The main quenching mechanism of the lanthanide emission appears to be due to vibrations among surrounding C–H bonds of the intermediate shell of the flexible dendrimer scaffold. Antenna effect and energy harvesting from the surface of the dendrimer and transfer to the core was the main mechanism for luminescecnce in the dendrimer complexes with lanthanide cations.