A series of novel hybrid poly(acetoxylstyrene-co-isobutylstyryl-POSS)s (PAS−POSS) and poly(vinylpyrrolidone-co-isobutylstyryl-POSS)s (PVP−POSS) are synthesized and characterized. The POSS content in these hybrids can be controlled by varying the monomer feed ratio. The polyhedral oligosilsesquoixane (POSS) moiety can effectively increase the Tg of the resultant organic/inorganic hybrid polymer at a relatively high POSS content and produce the hybrid copolymer with narrower molecular weight distribution. The FTIR spectra are used to investigate the structure−property relationship of these hybrid polymers, and the Tg enhancement mechanism is discussed in detail.