Polyelectrolyte complex membranes based on sodium cellulose sulfate as a polyanion and various types of cationic components - poly(dimethyldiallylammonium chloride), poly(ethyleneimine hydrochloride) as polycations; or (2-(N-undecylamidocarbonyl)-ethyl)-dimethylbenzyl ammonium chloride, N-dodecylpyridinium chloride as cationic surfactants were prepared. The membrane performances and selectivities in two pervaporation processes were tested. Results are discussed with respect to the surface characteristics of membranes, obtained from XPS, contact angle and tangential streaming potential measurements. Several important relations between membrane efficiencies or selectivities and surface characteristics were found.