In electrophoretic separators, a porous membrane is used to put into contact two flowing liquids between which an electrically driven mass transfer takes place. As far as charged solutes are concerned, the mass transfer can be affected by electrostatic interactions taking place at the membrane solution interface. The influence of these interactions on the solvent and solute transfer is investigated by associating a theoretical and an experimental work, carried out with buffered solutions of different solutes, chosen with respect to their size or electrical charge. Experimental variations of the electroosmotic flux as well as those of the solute concentrations are used to get the values of the characteristic parameters involved in the model. Results obtained with binary solutions are then compared to those obtained with single-solute solutions so as to point out the mass transfer limitation.