The interaction between poly(acrylic acid) polymers (PAA) of low- (2000 g/mol) and high- (450,000 g/mol) molecular weight (Mw) hydrophobically modified with pyrene (PAAMePy) and β- and γ-cyclodextrins (β-CD, γ-CD) was investigated with fluorescent techniques. The interaction with β-CD promotes little variation in the spectral and photophysical behavior of the polymer, whereas significant changes are observed upon addition of γ-CD. The degree of inclusion (between the pyrene groups of the polymer and the cyclodextrins) is followed through the observation of the changes in the absorption, excitation (collected in the monomer and excimer emission regions) and emission (IE/IM ratio) spectra and from time-resolved data. Within the studied range of γ-CD concentration, the fluorescence decays of the long chain (high Mw) PAAMePy polymers were found tri-exponential in the monomer and excimer emission regions in agreement with previous studies. In the case of the low Mw PAAMePy polymers, tri-exponential decays were observed at the monomer and excimer emission wavelengths. However, when a γ-CD concentration of 0.01 and 0.03 M is reached for, respectively, the low- and high-labeled pyrene short chain (low Mw) polymers, the fluorescence decays in the excimer region become biexponential (two excimers) with no rising component, thus showing that all pyrene groups are encapsulated (and preassociated) into the γ-CD cavity. In the case of the high Mw polymers, the addition of γ-CD has been found to change the level of polymer interaction from pure intramolecular (water in the absence of cyclodextrin) to a coexistence of intra- with intermolecular interactions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1402–1415, 2008