The interaction of hydrophobically randomly modified and end-modified poly(2-(acrylamido)-2-methylpropanesulfonate)s (PAMPSs) with nonionic and positively and negatively charged surfactants was studied with the fluorescence spectroscopic technique of labeled pyrene. The results indicated that the randomly modified PAMPS bound to the nonionic and positively charged surfactants and that the disruption of intrapolymer micelles formed by the polymer occurred. In contrast, end-modified PAMPS was bound to the surfactants without the disruption of multipolymer aggregates formed by the polymer in a comparably low concentration range of surfactants. The conformation of the polymer-surfactant complex was confirmed to depend on the position of the hydrophobic group in the polymer chains. In the case of negatively charged surfactant, the complex formation between the polymers and the surfactants was significantly restricted due to the electrostatic repulsion of anionic sites of the polymer chains and the negatively charged surfactants.