It has been first found that separated homopolymerization of an amphiphilic monomer, dodecylglyceryl itaconate (DGI), and acrylamide takes place even in one-pot radical reaction. The DGI molecules form a lamellar liquid crystal of bilayer membranes having the spacing distance of submicrometer and show the iridescent color in the presence of small amount of ionic surfactant. This colored bilayer system can be polymerized together with acrylamide and methylenebis(acrylamide) by photopolymerization to form a hydrogel containing the lamellar structure inside. In this polymerization process, the DGI molecules polymerize alone to form its homopolymer without reacting with any acrylamide and/ or methylenebis(acrylamide) molecules. This novel phenomenon has been substantiated by the experimental techniques of SDS-poly(acrylamide) gel electrophoresis, H-1 NMR, and IR spectroscopy. This novel homopolymerization of DGI may be resulted from the preferential bond formation between DGI molecules in their organized molecular assembly and is quite interesting with special reference to the chemical reactions in biological systems. The present reaction system may provide a simplest artificial model for the biological reactions in the complicated organized molecular assembling systems.