The encapsulation of the active layers (organic semiconductors, electrodes, transparent conductive oxides, etc.) of organic electronic devices developed onto flexible polymeric substrates is one of the most challenging issues in the rapidly emerging area of organic electronics. The importance for the protection of the active layers arises from the fact that these are very sensitive when they are subjected to the atmosphere, since the permeation of the atmosphere's water vapour (H2O) and oxygen (O$_{2})$ gases induces corrosion effects, film delamination and finally, failure of the organic electronic device. In addition, the encapsulation layers contribute to the long-term stability of the whole device enabling its use in outdoor environments (e.g. in the case of flexible photovoltaic cells-OPVs). A promising approach for the encapsulation of flexible organic electronics includes the development of multilayers that consist of hybrid polymer materials and inorganic layers onto flexible polymeric substrates, such as poly(ethylene terephthalate) (PET). This approach leads to a significant improvement of the barrier performance of the whole structure, due to the synergetic effect of the confinement of the permeation to the defect zones of the inorganic layer, and the formation of chemical bonds between the hybrid polymer and the inorganic layer. The knowledge of their optical properties and their correlation with their barrier performance are of major importance since it will contribute towards the optimization of their functionality. In this work, we provide an overview on the results concerning the use of hybrid polymers as ultra high barrier materials and moreover we discuss on the effect of inclusion of SiO2 nano-particles on their optical properties and barrier performance.