ABSTRACT Novel semi-interpenetrating polymer network (semi-IPN) anion-permselective membranes are prepared via a facile monomer sorption method. The base membrane is prepared by in-situ copolymerization of N,N’-dimethylaminoethyl methacrylate (DMAEMA) and divinylbenzene (DVB) in a non-porous poly(vinyl chloride) (PVC) substrate film (i.e. poly(DMAEMA-co-DVB)/PVC). The successive quaternization reaction along with di-functional p-xylylene dichloride forms the structurally stable anion-exchange groups that are fused with one another. Various characterizations (measurements of the transport number, electrical resistance, I-V curves, and chronopotentiometry etc.) reveal that the electrochemical properties of the prepared membranes are almost comparable with those of a commercial anion-exchange membrane (AMX, Astom Corp., Japan). In addition, the structural stability of the anion-exchange sites is confirmed through the water-splitting experiments at a high applied current condition.