A polyhedral oligomeric silsesquioxane (POSS)-based supramolecular amphiphile is prepared from the hostguest inclusion complexation between a mono adamantane-functionalized POSS (AD-POSS) and a beta-cyclodextrin oligomer (P(beta-CD)). Assisted by the interface of H2O/toluene, the obtained supramolecular hybrids self-assemble into stable hollow nanospheres with thick walls. These hollow nanospheres aggregate together into a sphere layer through a spin coating technique, which then further transforms into a thin porous film containing nanometer-scale holes. The hollow nanospheres have a low cytotoxicity. The in vitro cell culture indicates the nanoporous films promote adhesion and proliferation of cells. The self-assembly morphologies and structures have been carefully characterized by SEM, TEM, AFM, DLS, XPS and water-contact angle measurements, and the self-assembly mechanism has also been discussed.