Novel organic-inorganic hybrid nanocomposites have been obtained by the condensation polymerization of dibromoarene with octavinyl polyhedral oligomeric silsesquioxane via palladium-catalyzed Heck reaction. The structures of polymers are characterized by means of FT-IR, solid 13C, and 29Si NMR spectroscopy. The results show that the POSS building block was successfully weaved in the structure without obvious alteration of the characteristics and structure. TGA results show that polymers possess good thermal stability.