Polyacrylamide with well-defined polystyrene grafts (PAM-g-PS) and poly(methacrylic acid) with well-defined poly(methyl methacrylate) grafts (PMAA-g-PMMA) were synthesized via macromer techniques. Polymerization conditions and reactivity ratios for the copolymerizations were studied. The graft copolymers were purified by extractions and characterized with IR spectra. Structural parameters of PMAA-g-PMMA were determined by measurement of number average molecular weight of both macromers and copolymers. Both kinds of the graft copolymers are amphiphilic, exhibiting good emulsifying properties. When PAM-g-PS was mixed with PMAA-g-PMMA in a molar ratio of PAM/PMAA = 1, an intermolecular complex membrane was formed. This behaves as a chemical valve; its permeability can be controlled reversibly by changing the pH value.