The interaction of cationic surfactants, n-alkyltrimethylammonium bromide ($C_nTAB$; n = 12, 14, 16) with anionic polyelectrolyte, poly(styrenesulfonate) (PSS) has been studied by surface tension measurement. In the absence of added salt, the cationic surfactants bind to PSS quantitatively up to ca. 60% coverage of anionic sites of the polyanion and the complexes were surface inactive. Further binding of the surfactant cations on PSS caused a sharp conformational transition of the surfactant/ PSS complexes to surface active complexes and accompanied precipitation. The binding showed a biphasic behavior in the presence of NaCl and cooperativity of the binding became less as the concentration of NaCl increased. Binding of the cationic surfactants on poly(vinylsulfonate) also showed the biphasic behavior and the cooperativity of the binding was much less even in the absence of NaCl. The binding of surfactant to PSS provided hydrophobic environment to solubilized pyrene and reduced the viscosity of the solution greatly even at surfactant concentrations well below cmc. This study indicated that the surfactant bound to PSS up to $60{\%}$ coverage of PSS sites are present as surfactant aggregates which are wrapped up with PSS chains, and hydrophobic interaction is an important factor in the binding of the surfactants to PSS.