Excitation energy transfer (EET) in host–guest complexes of dansylated POPAM dendrimers and xanthene dyes have been studied by transient absorption spectroscopy. EET from dansyl periphery to guests: rose bengal, eosin, or fluorescein, showed non-exponential behaviour as a result of distribution of donor–acceptor distances. Time constants range from 100fs to 8ps, independent of the dye and the dendrimer generation. Experiments suggested that in dendrimers binding more than one guest, EET among the guests becomes effective. Guest–host and guest–guest interactions induce non-radiative relaxation channels making excitation decays of the guests clearly faster in complexes than in solution.