The effect of the conditions of formation of liquid membranes on the selectivity of dialysis and electrodialysis transfer of cations was studied. It was shown that the selectivity of membrane transport is determined by the structure of the macroheterocyclic complexones and the nature of their heteroatom. It was found that having information on the ion permeability orders of modified liquid membranes makes it possible to rationally select the solutions of electrolytes in the chambers of the electrodialyzer which ensure 90-99% extraction of the target component.