Membrane fouling is one of fatal barriers in electrochemical water treating technologies using ion exchange membranes (IEM) such as electrodeionization (EDI), Electrodialysis (ED), capacitive deionization (CDI), and reverse electrodialysis (RED). Calcium and Magnesium ions are representative foulants which make cake-like scale on the IEMs, leading to high resistance and low durability. In order to minimize membrane fouling in systems using IEMs, we are having developed monovalent cation selective membranes prepared by a layer-by-layer pore-filled technique. Anion exchangeable electrolytes are pore-filled on both surfaces of a semi-pore-filled cation exchange membrane (layer-by-layer). A porous PE substrate (<20 um) is used to be filled with electrolytes and crosslinking agents and to be polymerized. Monovalent cation selectivity against divalent ions, calcium and magnesium ions, of the resulting membranes was evaluated using 1N MgCl₂, CaCl₂ and NaCl solutions.