Four types of hydrophilic gel microcapsules containing water have been prepared by an interfacial polymerization method. Each type of microcapsules has membranes of different compositions, Using three kinds of monomers, N,N-dimethylacrylamide (DMAAm), 4-aminomethylstyrene (AmSt), and N,N-dimethylaminopropylacryramide (DMAPAA), two types of water-soluble copolymers with different compositions having primary and tertiary amino groups were obtained. Two more types of copolymers were synthesized by copolymerization of alpha-acryloxy-omega-methoxypoly(ethylene glycol) (a-PEG) with the above two kinds of monomer mixtures. These copolymers were polymerized with terephthaloyldichloride at the water/oil interface to prepare four types of microcapsules containing water. By electrophoretic mobility measurements of these microcapsules and the analyses of the data, it was found that the surface layer of the microcapsule membranes were composed of two sublayers, each of which has different charge density and softness. The outer sublayer was negatively charged and inner sublayer was positively charged. By PEGylation, the charge density in the outer sublayer decreased, while that in the inner sublayer was not affected. Also, the surface layer became softer by PEGylation, The effects of membrane composition upon the swellability of the microcapsule membrane were studied, It was found that the asymmetrical structure of the microcapsule membranes causes the nonuniform distribution of charges and then the swellability of the microcapsule membrane changes depending on the permittivity of the dispersing medium,