The polyether–polyamide (PC-6) strongly absorbs sodium salts from their aqueous solutions. Membranes based on PC-6 and on its polymeric alloys with poly(vinylpyrrolidone) (PVP) are, however, much more permeable to water than to salts. The membrane permselectivity is due to the low mobility of the absorbed salts. Desorption experiments were conducted to determine the values of the diffusion coefficients of the sodium ions in the investigated membranes. They were found to vary from 5 × 10-12 cm2/sec in loose PC-6 membranes to 1.7 × 10-9 cm2/sec in the polymeric alloy containing 30% PVP. Water permeation experiments with the alloy membranes yielded values of the diffusion coefficients in the range of 2–5 × 10-7 cm2/sec. The apparent “energy of activation of the diffusion” of sodium ions in such membranes was found to be essentially indentical (∼12 kcal) with the energy of activation of the decomplexation of the sodium–“crown” complex. The ramifications of the proposed “site to site jump” diffusion mechanism were discussed. The permeability characteristics of PC-6 membranes were found to be strongly affected by their “history.”. The observed phenomenon was explained in terms of reversible changes in the structure of the polymeric network, in the presence and in the absence of the absorbed salts. It has been found that PVP has a stabilizing effect on the permeability characteristics of the membranes. Reverse osmosis experiments indicated that their intrinsic osmotic characteristics seem to be superior to those of the commercially used materials. Their salt rejections are in the range of 95–99.5%, and their permeabilities to water are at least one order of magnitude higher than those of the unmodified aromatic polyamides.