Sol-gel is a wide-spread methodology for low-temperature synthesis of ceramics, nanocomposites and hybrid (inorganic-organic) materials. Ormosil (Organically Modified Silicates) belong to these class of hybrid materials, which have potential uses as optical materials, chemical sensors, catalysts, membranes, self-cleaning coatings. We are especially interested on the application of Synchrotron Radiation X-ray Microfluorescence (SR-μXRF) for the non-destructive analysis of such materials, benefiting of the high intensity obtained from this source of X-rays. SR-μXRF has demonstrated to be a useful analytical tool for qualitative and semi-quantitative determination of Hybrid films containing phosphotungstates ([PW<sub>12</sub>O<sub>40</sub>]<sup>3-</sup>/PWA), in order to determine the local concentration, as also the correlation among elements. For ormosil films, SR-μXRF enabled the qualitative determination of Titanium (Ti) that is heterogeneously distributed, oppositely to the case of Zinc (Zn) and Tungsten (W). For PI-ORMOSIL-PWA films, SR-μXRF maps have shown the heterogeneous distribution of the Silicon (Si) and a quasi-homogenous distribution of Tungsten (W). SR-μXRF results for Silicon (Si) and Tungsten (W) are consistent with the corresponding concentrations obtained by ICP-OES analyses, which were taken as the reference results. For PDMSUr-PWA films, SR-μXRF mapping have shown the heterogenous distribution pattern for Tungsten (W) and the capacity for the identification of Bromine (Br). For these materials NAA analyses were taken as the reference results for Tungsten (W). Furthermore, they are presented the HorRat parameters, in order to estimate approximately the degree of heterogeneity of these materials, which are in agree with the observed in the corresponding mappings obtained by SR-μXRF, giving hints about segregation at surface and at bulk level. HorRat parameters for concentrations obtained by ICP-OES and NAA (bulk analyses) are close to the expected value (2.0), which make possible using as reference values for SR-μXRF results (analyses at surface and medium-bulk levels), due to the non-existence of standards for these hybrid materials (at Micro- and Nano-Scale).
