Abstract: Polyhedral oligomeric silsesquioxanes (POSS) is a typical nano-structured organic/inorganic particle with inner Si—O—Si caged structure bearing one or more functional groups R attached to its top corners as the general formula (RSiO1.5)8. POSS can be incorporated into apolymer matrix by the chemical functionalization of one or more functional groups into the corner of the POSS chemical structure, and therefore self-assembled into wettibility surface. This paper mainly introduced the structure features of POSS, the synthesis, assembled micelles and surface wettibility of POSS-based fluoropolymers. The protective performance of two POSSbased fluoroplymers to the sandstone and cottonfiber is also evaluated.