The interactions of hydrophobically random-modified and end-capped poly(2-(acrylamido)-2-methylpropanesulfonate)s (PAMPSs) with the nonionic surfactant dodecyl hexa(oxyethylene) glycol monoether (C12E6) were investigated by fluorescence spectroscopic technique of labeled pyrene. The results revealed that the random-modified PAMPS interacts with C12E6 and that the intrapolymer micelle formed from the polymer gets disrupted. In contrast, the end-capped PAMPS interacts without disruption of the multipolymer aggregate formed from the polymer at a comparably low concentration range of C12E6. The conformation of the polymer surfactant complex depends on the position of the hydrophobic group in the polymer chains.