In this paper, we focus on improvement of the monovalent cation perm-selectivity of a perfluorinated cation-exchange membrane, Nafion 117, by depositing an anion-exchange layer using a plasma surface modification process. The anion-exchange layer was deposited from 4-vinylpyridine monomer vapor followed by quaternization with 1-bromopropane. The transference number of divalent cation (Fe2+) through the membrane, t(Fe), decreased with increasing thickness of the plasma polymer layer at the expense of enhanced membrane resistance. A large interfacial resistance was observed between Nafion and the plasma polymer layer which was ascribed to the implantation of cationic species containing nitrogen. To avoid the formation of an interfacial layer, a novel method of plasma-induced surface modification was devised. After a Nafion 117 sheet was placed on an RF (radio-frequency) electrode and sputtered with an oxygen or argon plasma in order to produce active sites on the Nafion, 4-vinylpyridine or 3-(2-aminoethyl)aminopropyltrimethoxysilane vapor was introduced into the reactor to react with radical sites. t(Fe) decreased with increasing RF power. t(Fe) through Nafion modified with 3-(2-aminoethyl)aminopropyltrimethoxysilane was lower than that for Nafion modified with 4-vinylpyridine, probably due to its weak Si-C bond. Nafion treated by the plasma surface modification method exhibited a very high monovalent cation perm-selectivity compared with Nafion treated by the plasma polymerization method.