In this investigation the surface properties optimisation of a flexible PEN foil to use as substrate for thin film silicon solar cells is presented. The polymer surface, usually hydrophobic and inactive to chemical reactions, can give poor adhesion for films deposited on it. Furthermore, gas desorption from the polymer sometimes causes serious problems to the quality of the devices. To overcome these problems a thin film of silica-like functional material has been developed on polymer foil. Silica-like films were produced by sol-gel process starting from an organic silanes compound (APTMS) as precursor and the solution was deposited by spin-coating. Amorphous silica-like films were obtained with a hydrophilic surface. They were smooth, dense, homogeneous, transparent and exhibited an excellent adhesion to the polymer substrate due to the chemical bond between amine groups of the APTMS with carbonyl bonds in PEN. Physical properties such as elastic modulus and hardness and the UV irradiation effect on structure and surface hydrophilicity of the silica-like coatings have been analysed. A water contact angle of 34° was obtained after UV irradiation. Nanoindentation analysis showed that the silica-like coating have an hardness and an elastic modulus up to 2.0 GPa and 13.2 GPa respectively much higher than that of pure PEN. Oxygen permeability measured on silica-like coated PEN gave a value of 5.7 x 10-9 cc m/m2 s atm showing larger barrier properties respect to pure PEN. Strong adhesion, improved mechanical properties and barrier effect of our silica-like coating make the modified PEN substrate suitable to be used in thin film solar cell technology.