Hard X-rays, deriving from a synchrotron light source, have been used as an effective tool for processing hybrid organic-inorganic films and thick coatings up to several micrometres. These coatings could be directly modified, in terms of composition and properties, by controlled exposure to X-rays. The physico-chemical properties of the coatings, such as hardness, refractive index and fluorescence, can be properly tuned using the interaction of hard X-rays with the sol-gel hybrid films. The changes in the microstructure have been correlated especially with the modification of the optical and the mechanical properties. A relationship between the degradation rate of the organic groups and the rise of fluorescence from the hybrid material has been observed; nanoindentation analysis of the coatings as a function of the X-ray doses has shown a not linear dependence between thickness and film hardness.