Slightly cross-linked polyelectrolytes absorb oppositely charged surfa
ctants in aqueous media. Transfer of amphiphilic ions from solution in
to the swollen network proceeds as a frontal heterogeneous cooperative
reaction causing a collapse of the original polyelectrolyte gel. Smal
l and wide angle X-ray diffraction data show that electrostatic comple
x formed as a result of the reaction consists of lamellar type surfact
ant micelles embedded in a polyelectrolyte network. It is also shown t
hat such complexes contain equimolar amount of surfactant ions and ion
ized polyelectrolyte units paired with amphiphil head groups. In other
words a charged network is not able to bind surplus oppositely charge
d surfactant ions. However, it is still able to solubilize a substanti
al amount of a nonionized surfactant. Chemical structure of surfactant
s strongly affect internal structure of lamellae and stability of the
complexes.