In this presentation, we proposed two POSS-containing block copolymers. Firstly, we used a combination of atom transfer radical polymerization, ring opening polymerization, and click chemistry to synthesize new organic/inorganic macromolecular self-assembling building blocks of PS-b-(PPLG-g-POSS). Secondly, we prepared PMMA-b-PMAPOSS block copolymers of various compositions through anionic living polymerization. The hierarchical self-assembly structures of POSS-containing block copolymers were characterized using wide-angle X-ray diffraction, small-angle X-ray scattering, and transmission electron microscopy, led to the formation of cylindrical structures as a result of microphase separation of the diblock copolymer; the hexagonal cylinder packing nanostructure featured α-helical conformations of polypeptide or PMMA segments, which were oriented perpendicular to the director the cylinder column from diblock copolymers; aggregation of the POSS moieties induced the packing into hexagonal lattice structures.