The development of high barrier films for the encapsulation of organic electronics devices onto flexible polymeric substrates is attracting a considerable scientific interest, since it is important to protect the organic semiconductor layers of these devices from corrosion due to atmospheric gas molecule permeation. The barrier layers for encapsulation consist of a sequence of inorganic and hybrid polymer thin films that are deposited onto flexible polymeric substrates, such as polyethylene terephthalate (PET). In addition to their barrier response, these multilayer systems should also exhibit high transparency and good adhesion between the hybrid polymer and inorganic layers. The knowledge of their optical properties and the correlation of the optical response with their structure and the final barrier response are of major importance since it will contribute towards the optimization of their functionality. In this work, the optical properties of hybrid polymers deposited onto silicon oxide inorganic thin films that were grown onto flexible polymeric substrates, have been investigated by the use of spectroscopic ellipsometry in a wide spectral region from the infrared to the visible-ultra violet. As it has been found, the increase of the solid content in the hybrid polymers is associated with a reduction in the refractive index values. This behavior can be correlated to a lower density of the hybrid polymer, and furthermore to a poor barrier response, due to the less cohesive inorganic-organic bonding network. Finally, from the investigation of the optical response of the hybrid polymers in the IR spectral region has revealed information on their bonding structure that has been discussed together with their barrier response. (C) 2009 Elsevier B.V. All rights reserved.