An extensive study by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) of some first-generation and second-generation lanthanide(III)-cored poly(phenylenevinylene) dendrimers is described. The complexes were obtained by self-assembly of suitably functionalized carboxylate dendrons around the lanthanide ion (La(3+), Er(3+)). Fourier transform infrared (FT-IR) spectroscopy gave reasonable evidence for the proposed structures. However, MS was used to ascertain unequivocally the complex formation. The most reliable results were found in the negative reflector mode, using 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB) as matrix. Well-defined and highly resolved base peaks corresponding to negative ions of [Gn(4)La](-) and [Gn(4)Er](-) were found in all cases, with an excellent match between the theoretical and observed isotope distributions. However, the 3:1 stoichiometry used in the synthesis guarantees an empirical formula Gn(3)Ln for the complexes.