Polysilsesquioxanes (PSQs) possessing 3-methacryloxypropyl groups as an organic moiety of the side chain were synthesized by sol-gel condensation copolymerization of the corresponding trialkoxysilanes. The ultra-thin PSQ film with a radical initiator and a cross-linking agent was prepared by a spin-coating method, and the film was cured integrally at low temperatures of less than 120 degrees C through two different kinds of polymeric reactions, which were radical polymerization of vinyl groups and sol-gel condensation polymerization of terminated silanol and alkoxy groups. The obtained PSQ film showed the almost perfect solubilization resistance to acetone, which is a good solvent of PSQ before polymerization. It became clear by atomic force microscopy observation that the surface of the PSQ film was very smooth at a nano-meter level. Furthermore, pentacene-based organic field-effect transistor (OFET) with the PSQ film as a gate insulator showed typical p-channel enhancement mode operation characteristics and therefore the ultra-thin PSQ film has the potential to be applicable for solution-processed OFET systems. (C) 2012 Elsevier B.V. All rights reserved.