Novel class of active ionophores for surfactant selective electrodes is proposed. PVC membrane doped with polyelectrolyte–surfactant stoichiometric complex is used for ion-selective electrode construction responsive to cetyltrimethyl ammonium bromide and related surfactants. New ionophore is quite stable and completely insoluble in aqueous media in wide range of pH. The electrode displays nearly Nernstian slope in CTAB concentration range 10−6–10−3 M. Polyelectrolyte platform allows to design wide range of different ionophores responsive to cationic organic substances.