The mechanical properties and thermal stability of polymers can be enhanced through the formation of nanocomposites. Nanocomposites consisting of hybrid copolymers of methacrylcyclohexyl polyhedral oligomeric silsesquioxane (POSS-1) and methyl methacrylate (MMA) with up to 92 wt % (51 mol %) POSS-1 and with superior thermal properties were synthesized using solution polymerization. The POSS-1 contents of the copolymers were similar to or slightly higher than those in the feeds, the polydispersity indices were relatively low, and the degree of polymerization decreased with increasing POSS-1 content. POSS-1 enhanced the thermal stability, increasing the degradation temperature, reducing the mass loss, and preventing PMMA-like degradation from propagating along the chain. The mass loss was reduced in a high POSS-1 content copolymer since the polymerization of POSS-1 with itself reduced sublimation. Exposure to 450 degrees C produced cyclohexyl-POSS-like remnants in the POSS-1 monomer and in all the copolymers. The degradation of these remnants, for the copolymers and for the POSS-1 monomer, yielded 75% SiO2 and an oxidized carbonaceous residue. (c) 2007 Wiley Periodicals, Inc.