The aim of this work was to create new polymer membranes with a hierarchical structure, namely, the creation of multilayer membranes prepared by physical adsorption technique. The upper selective layer was applied by interfacial polymerization. As polymeric ultrafiltration substrates were used polyacrylonitrile, polyphenylene isophthalamide, and regenerated cellulose. As an intermediate polymer layer were used chitosan, polyallylamine hydrochloride, polyphenylene isophthalamide. It was shown that the creation of multi-layers led to an increase in the efficiency of separation of organic and water-containing binary mixtures.