Hybride nanocomposite films of polyhedral oligomeric silsesquioxane (POSS) and polyurethane acrylate (PUA) were prepared by introducing POSS into PUA by free-radical photopolymerization, to enhance thermo-mechanical properties of PUA. The addition of POSS to PUA resulted in increases in the following properties: elasticity, glass transition temperature, thermal stability and dimensional stability. With increasing POSS content, the elastic modulus and thermal stability of PUA films increased due to an increased crosslinking density and the reinforcing effect of POSS particles on the PUA, whereas the surface free energies of these films decreased. The water contact angle against water increased due to the enhancement of the hydrophobicity of the polymer surface, caused by the low surface energy of POSS molecular. However, at high POSS content the mechanical properties of the films were decreased, as a result of aggregation of the POSS particles.