Surface polyion complex (sPIC) gels were prepared with a nonionic hydrogel interior core, composed of poly (N-vinylformamide and poly(N-vinylacetamide), and a chemically bounded polyion complex layer on the outer surface, composed of poly(vinylamine) and poly(acrylic acid). The gels were investigated as controlled drug release models based on electrostatic interactions depending on pH. Methylene blue and allura red were employed as cationic and anionic drug models, respectively, and resulted in the selective adsorption depending on pH conditions. Monovalent and multivalent anionic drug models, allura red and 1,3,6-naphthalenetrisulfonate were observed for their releasing behavior from the sPIC gel. The results indicated that the multivalent anionic drug effectively controlled release depending on pH conditions. We further investigated sPIC gels regarding their ability to control the release of ionic molecules as a function of pH-driven changes in electrostatic interactions. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42081.