Nonstoichiometric ordered network polymer-surfactant complexes (NPSC) formed by slightly cross-linked networks of poly(diallyldimethylammonium chloride) (PDADMACL) and oppositely charged surfactant of sodium dodecylbenzenesulfonate (SDBS) were obtained. The structure of NPSC was studied by SAXS. At the excess of SDBS in the presence of low-molecular-weight salt, sodium chloride, the complexes can include the surfactant molecules containing sodium ions. The structure of such nonstoichiometric NPSC is more ordered than that of NPSC prepared in the absence of salts. The excess of the surfactant anions in polyelectrolyte network increases in the region of intermediate NaCl concentration (ca. 0.3 M). At a very high concentrations of NaCl (ca. 1.0 M) partial dissociation of the complex and formation of SDBS precipitate in the solution with lamellar type of ordering is observed.