Optical resolution by membrane permeation is a very effective continuous method compared with conventional batch methods. We previously reported some optical resolution by simple permeation through chiral poly (substituted acetylene) membranes. In this study, the performances have been improved by the following two methods. One is enantioselective imine exchange reaction of the side imino groups of the polymer membranes with a racemic chiral amine as permeants during permeation. The other is permeation through new composite membranes containing supramolecular polymers by partial in-situ decomposition reaction of the polymer membranes. As a result, permselectivity was enhanced up to 88.5%ee for (RS)-phenylethylamine (PEA).