Hydrophilic ionic polyurethanes with 4-chloromethylphenylcarbamoyl-1-oxymethylpyrene located on the quaternary ammonium structure from a polymer based on poly(ethylene glycol), isophorone diisocyanate, and N-methyldiethanolamine were prepared by a quaternization reaction, in which the amount of pyrene covalently attached to the polymeric backbone ranged from 1.14 to 19.82 mmol of fluorophore/100 g of polymer. It was interesting to compare the photoluminescence of the pyrene polyurethane carrying a few mole percent of pyrene moieties with that of a third polymer resulting from its subsequent quaternization with benzyl chloride up to a concentration of ionic groups as in the latter (quaternization degree = 14.15%). The process of excimer formation between the pyrene molecules attached to the ionic polyurethane was investigated in tetrahydrofuran (THF), dimethylformamide, film, and THF/H2O to illustrate the expected differences in the polymer behavior compared with that of the starting pyrene derivative. The formation of aggregates or core-shell micelles was sustained by the fluorescence data, which indicated the existence of pyrene units in the ground state of the molecule, giving rise thus to an explanation for the high excimer-to-monomer intensity ratio. The fluorescence decay of pyrene polyurethanes in the presence of various concentrations of nitrobenzene used as a quencher was analyzed too when the fluorescence quenching in the polymer solution normally followed Stern-Volmer kinetics. (c) 2005 Wiley Periodicals, Inc.