One of the major scientific and technological challenges for the production of flexible organic electronic devices is the device protection against atmospheric molecule permeation, which causes corrosion reducing its operation and lifetime. In this work, Spectroscopic Ellipsometry has been implemented to investigate the influence of silicon dioxide nanoparticles on the optical properties of hybrid polymers. The spectra analysis revealed valuable information about the electronic and vibrational response as well as the cross-linking mechanisms of these materials. The correlation of the optical properties with the synthesis parameters and the barrier response will contribute towards their optimization in order to be used as high barrier coatings for flexible organic electronics applications. (C) 2009 Elsevier B.V. All rights reserved.