Polyhedral oligomeric silsesquioxanes (POSS) have been considered as fascinated synthetic organic-inorganic precursor materials in the field of advanced materials science owing to their superior physicochemical properties, including high thermal and mechanical, low dielectric and surface properties, low moisture absorption, and high photoluminescence properties. The high-performance properties, as well as their well-defined organic-inorganic nanoscaled structure, contribute to the building of nano-structured polymeric hybrid materials and nanocomposites for a wide range of industrial and engineering applications. In this chapter, spectroscopic analyses of different types of POSS-based hybrid polymeric materials are discussed.