Hybrid films prepared from TEOS and polyoxazolines (Si–POx–Si) crosslinking agents were coated on different substrates in order to modify their surface properties. The film cohesion and adhesion on substrates were expected through the hydrogen bonding of the polyoxazoline crosslinked network. Low molecular-weight α,ω-unsaturated polyoxazolines (DA-PMOx)s were synthesized by a one step cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline (MOx) with a good control over the molecular weight. Based on double thiol-ene coupling (d-TEC) a post-functionalization of DA-PMOx end chains gave in good yield polyoxazoline cross linker (Si–POx–Si). Glass and various polymer substrates (PP, PEI, POM, etc.) were spin coated by the organic–inorganic hybrid films through sol–gel process. AFM, SEM, visible reflectance spectroscopy and contact angle experiments allowed the full characterization of targeted surfaces and demonstrated the efficiency of the polyoxazoline coating.