A free-standing, roll-able, and transparent silicone-based polymer film with a tensile modulus of ca. 7.8 MPa and strain at the break point of 0.76% was successfully prepared by reaction between a reactive silicone oligomer with methyl- and methoxy-side groups and hydrophilic SiO2 nanoparticles. First, SiO2 nanoparticles were grafted with silicone chains by a controlled wet chemical sol-gel-type reaction with the reactive oligomers. The solvent of the resulting solution was evaporated to form a viscous suspension, casted into a film, and finally heat-treated at 100 degrees C and 150 degrees C. A hydrolysis and condensation reaction among silicone-grafted SiO2 nanoparticles and free silicone oligomers in the final heat treatment resulted to produce free-standing, roll-able, and transparent silicone-based polymer film. The fact that the silicone film cannot be synthesized without the presence of SiO2 nanoparticles suggests that these nanoparticles act as cross-linking agents of silicone components providing the improved mechanical properties to the composite film. The rate-controlled mixing and heating of the SiO2 aqueous/alcohol suspension and the silicone oligomer/alcohol solution was found to be the key step in the synthesis of the free-standing transparent film. While rapid addition/mixing resulted in a fragile and opaque film, a transparent material was achieved when those solutions were slowly mixed. The effect of the synthesis process on the macroscopic and microscopic properties of the prepared films is discussed along with their formation mechanism. (C) 2012 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.