The change of interactions of anionic surfactants, sodium dodecyl sulfate(SDS) and sodium tetradecyl sulfate(575) in the presence of electrolytes, to the chitosan-based polyelectrolyte(sol＇n and gel phase) were studied. The chitosan gel used in this study were crosslinked with epichlorohydrin(ECH). Binding isotherms were determined by potentiometric technique using a surfactant ion selective solid-state electrode and the results were represented by using the sequence generating function(SGF) method. The results of binding isotherm were shown comparatively high cooperativity. The addition of electrolytes in the chitosan/SDS system resulted in a shift of the binding to higher free surfactant concentration because of screen effect by the electrolytes. Degree of binding of chitosan gel was higher than that of chitosan sol＇n. And also a conformational phase transition of the chitosan gel in the presence of electrolytes has been investigated.