Conventional sol-gels are rather hydrophilic. A more hydrophobic material is obtained preparing organically modified siloxanes (ormosils). The polarity-sensitive probe Nile Red (NR) was doped in various sol-gels to probe their micro-polarity. The experiments show that the NR is an excellent probe and sensitive to the polarity of its microenvironment. Spectroscopic studies reveal remarkable changes in the absorption band positions and intensities as a function of the polarity of the sol-gel, which depends on the different precursors used. Furthermore, sol aging, gelation and temporal stability as a function of different ormosils have been investigated.