The hydrodynamic behavior of aqueous solutions of poly(vinyl alcohol) and poly(vinyl alcohol)-cupric complex and its effect on the performance in the concentration of the macromolecular cupric complex by ultrafiltration is considered in this study which implements various synthetic membranes in polyethersulfone. The polyelectrolyte-like behavior of poly(vinyl alcohol) is highlighted. This behavior disappears in the case of the macromolecular complex. The disappearance of the polyelectrolyte-like effect is explained by the modification of the macromolecular conformation induced by the formation of the complex which takes up a tightly packed conformation. The study of the effect of the variation of the pH and the ionic strength made it possible to observe that the increase of the pH is accompanied by the reduction of the medium viscosity and the increase of the flux through the ultrafilters and the increase of the ionic strength of the medium is accompanied by the increase of the thickness of the adsorbed solute layer. The study of the effect of the nature of the ionic species in solution on the hydrodynamic behavior of the aqueous solutions of the macrocomplex leads to the conclusion that the use of the cupric chloride salt, instead of the nitrate or the sulphate salts, in the preparation of the macrocomplex improves the hydrodynamic properties of the solution and enhances the performance of its treatment by means of the ultrafiltration process.