Polyelectrolyte-surfactant complex (PELSC) membranes were prepared by the interaction of the anionic groups of sodium cellulose sulfate (Na-CS) or sulfoethyl cellulose (SEC) with different types of cationic surfactants. The membrane properties were investigated using pervaporation (PV) experiments with different organic feed mixtures, containing methanol (MeOH) as a polar component. Methanol was mixed with cyclohexane, methyl-t-butyl ether (MTBE), and dimethylcarbonate (DMC). The results of the separation experiments employing the methanol-containing mixtures show that the membranes reveal both very high permselectivity and permeability even at moderate temperatures.