Toward complete artificial photosynthesis systems to generate hydrogen and oxygen using visible light and water, oxygen-generating gel systems are designed and fabricated using the electrostatic interactions of ionic functional groups and steric effects of a polymer network. By using a graft polymer chain with Ru(bpy)(3)(2+) units as sensitizers to closely arrange RuO2 nanoparticles as catalyst, the functional groups transmit multiple electrons cooperatively to generate oxygen. In this paper, a novel strategy is shown to design a hierarchical network structure using colloidal nanoparticles and macromonomers. Such soft material to oxidize water inside a hydrogel is useful as a solar-energy converting system.