This review describes the syntheses of polyhedral oligomeric silsesquioxane (T8-POSS) compounds, the miscibility of POSS derivatives and polymers, the preparation of both multifunctional and monofunctional monomers and polymers containing POSS including styryl-POSS, methacrylate-POSS, norbornyl–POSS, vinyl-POSS, epoxy–POSS, phenolic–POSS, benzoxazine–POSS, amine-POSS, and hydroxyl-POSS. The thermal, dynamic mechanical, electrical, and surface properties of POSS-related polymeric nanocomposites prepared from both monofunctional and multifunctional POSS monomers are discussed. In addition, we describe the applications of several high-performance POSS nanocomposites in such systems as light emitting diodes, liquid crystals, photo-resist materials, low-dielectric constant materials, self-assembled block copolymers, and nanoparticles.