The process of complex formation and the structure of the complexes were studied for the surfactant binding of the N-alkylpyridinium chlorides (CnPyCl, n = 12, 16) to the sodium salt of poly(styrenesulfonate) (NaPS) and its copolymer with styrene. Both the NaPS and the amphiphilic copolymer form non-stoichiometric complexes with an excess of the cationic surfactants. The NaPS-complex with pronounced short-range (d(1)) and long-range (d(2)) orderings is insoluble, and the amphiphilic copolymer-complex is water-soluble when bound with extra charges. The mechanism of the complex formation was discussed in terms of the charge density and chemical composition of the polymers.