The previously presented bicompartmental models for intramolecular excited-state systems with added quencher [Boens et al. J. Phys. Chem. 1993, 97, 799 and Van Dommelen et al. J. Phys. Chem. 1993, 97, 11738] are experimentally investigated by time-resolved fluorescence measurements. The emission of the bichromophore bis(2-pyrenecarboxylic acid) 1,6-hexanediyl ester was studied in the absence and presence of iodomethane as a fluorescence quencher. Two different approaches are examined : one where no information is known beforehand and another where the time-resolved emission from the model compound hexyl 2-pyrenecarboxylate was used in the fittings. In the first approach, it was possible to obtain upper and lower limits for the rate constants k(01), k(21), k(02), and k(12) (see Scheme 1) by analyzing at different preset values of the rate constant k(01). For the other approach, the parameter values of k(01) and k(Q1) were defined by linking these parameters with the corresponding rate constants of the model compound, whose quenched decays were included in the data analysis. For the calculations of the species-associated emission spectra (SAEMS) two different strategies were followed in the data analysis : one where no information from the model compound steady-state fluorescence spectra was included and one which made use of such information. SAEMS were obtained for both strategies, but inclusion of the steady-state fluorescence spectra information leads to better defined SAEMS for the locally excited state and excimer emissions.