We report on the attachment of polymer monolayers or surface-attached, polymer networks onto SiO2 and/or polymer surfaces using thermo- and photoreactive alpha-diazoester groups. In the prior case, the alpha-diazoester groups are introduced into the system in the form of self-assembled monolayers of appropriately functionalized silanes. The monolayer decorated substrates are coated by polymer films and the alpha-diazoester groups in the monolayer are activated by heat or irradiation with UV-light Upon activation, they cleave off nitrogen and the resulting carbene intermediates insert into C-H bonds of neighboring polymer chains. As a result of this binding process, surface-attached monolayers of the deposited polymer are obtained. When the polymers themselves carry such reactive moieties, the photo- or thermal activation leads to cross-linking of the polymers and thin surface attached polymer networks result from the same process. The formation of the surface attached layer is studied as a function of activation conditions, especially the temperature and the wavelength of the light used in the process.