Insoluble nonstoichiometric and stoichiometric complexes were formed as a result of reaction between polystyrene-bloch-polyacrylate anions (PS-b-PAA(-)) and N-cetylpyridinium cations (C16Py+) in aqueous media. In the presence of water the nonstoichiometric complexes with low content of surfactant represent swollen materials that contain polystyrene fragments, PAA units neutralized by surfactant, and ionized PAA(-) chains capable of ion exchange reactions involving regular inorganic and surfactant counterions. In the solid state these complexes represent a special class of complex ionomer material containing a segregated crystalline domain from C16Py+ bound to the polyion, sodium-carboxylate ion pairs, and an amorphous polystyrene segment. Changing the polyion and surfactant ratio as well as lengths of the block ionomer segments can vary the microstructure of such materials and their properties.