We report on a simple and effective way to attach thin polymer films to solid surfaces. The system is based on a thermosensitive sulphonyl azide derivative that is immobilized to SiO2 surfaces via chlorosilane anchoring group and subsequently covered with a polymer film. Upon heating the sulfonyl azide decomposes, leading to a C-H insertion reaction from the adjacent polymer chain resulting in a covalent attachment of the polymer to the surface. Any nonbound polymer can be removed by extraction. The method allows to attach a wide spectrum of polymers to solid surfaces. The film thickness of the monolayers can be tuned by adjusting the molecular weight of the polymer used and to some extent, the thermolysis conditions. The film thickness increases linearly with the radius or gyration of the polymers used for attachment. We have successfully attached thin layers of poly (styrene), poly (dimethylacryl amide) and poly (heptadecanfluorodecylacrylate).