New supramolecular assemblies based on cyclodextrin and adamantane were prepared. Two methacrylate monomers bearing cyclodextrin and adamantane were synthesized, and copolymerized with poly(ethylene glycol) methyl ether methacrylate, (PEGMA, 300 g/mol), by free radical polymerization. Copolymers bearing pendent cyclodextrin and adamantane were characterized by NMR, FTIR, TGA, SEC, Differential scanning calorimetry (DSC), and UV-visible spectrophotometer. All copolymers showed two distinct glass transitions. The specific interaction between pendent adamantyl and cyclodextrin was examined by H-1-NMR. The viscoelastic properties of supramolecular assemblies were investigated with frequency and temperature sweep experiments. The specific host-guest interaction between pendent adamantyl and cyclodextrin lead to large increases of the viscosity; and depending on the concentration of these groups, also to gel formation. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 581-592, 2010