Films and monoliths, containing clusters (sizes < 5 nm) of the binary semiconductor CdS and sandwiched CdS-PbS, were prepared via multifunctional inorganic-organic sol-gel processing. As a sulfur source, hexamethyldisilylthiane was employed. In precursor sols, the metal sulfide clusters are carrying functionalized silanes acting as stabilizing centers as well as inorganic and organic network formers. Hydrolysis and condensation produces an inorganic network yielding viscous liquids useful to prepare optically transparent films or monoliths. The final organic cross-linking at T < 100°C results in materials of variable spectral response, thickness and optical density. In preliminar degenerate four-wave mixing experiments, self-diffraction from laser-induced gratings was observed on unsupported 200 μm thick CdS-PbS doped monoliths. The maximum first order grating efficiency, measured at different wavelengths between 490 and 520 nm, was 0.5 · 10−3 and the corresponding calculated effective third order susceptibility was of the order of 10−9 esu.