In this study, we used click chemistry to synthesize a new macromolecular self-assembling building blocks, linear polypeptide-b-polyhedral oligomeric silsesquioxane (POSS) copolymers, from a mono-azido-functionalized POSS (N-3-POSS) and several alkyne-poly(gamma-benzyl-L-glutamate) (alkyne-PBLG) systems. The incorporation of the POSS unit at the chain end of the PBLG moiety allowed intramolecular hydrogen bonding to occur between the POSS and PBLG units, thereby enhancing the alpha-helical conformation in the solid state, as determined through Fourier transform infrared spectroscopy and wide-angle X-ray diffraction analyses. POSS-b-PBLG underwent hierarchical self-assembly, characterized using small-angle X-ray scattering, to form a bilayer-like nanostructure featuring alpha-helical or beta-sheet conformations and POSS aggregates. Thermogravimetric analysis indicated that the thermal degradation temperature increased significantly after incorporation of the POSS moiety, which presumably formed an inorganic protection layer on the nanocomposite's surface. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2127-2137, 2011