Head diversification of shape amphiphiles not only broadens the scope of supramolecular engineering for new self-organizing materials but also facilitates their potential applications in high technologies. In this letter, T10 azido-functionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle was used to construct new shape amphiphiles via sequential "click" chemistry for addressing two issues: (1) new symmetry of T10 POSS head could enrich the self-assembly behaviors of shape amphiphiles, and (2) copper-catalyzed azide-alkyne cycloaddition (CuAAC)-based head functionalization strategy allows the introduction of diverse functionalities onto POSS heads, including bulky ligands (i.e., isobutyl POSS) and UV-attenuating ones (i.e., ferrocene and 4-cyano-4'-biphenyl). This study expands the library of POSS-based shape amphiphiles with numerous possibilities for head manipulations, offering an important step toward new shape amphiphiles beyond traditional hydrophobic/hydrophilic nature for potential applications in giant molecule-based nanoscience and technology.