The optical properties of extremely small particles of semiconductor materials provide a sensitive probe of the band structure in the materials. The Sol-Gel process has been applied successfully to the preparation of small particle-size CdS-doped silica glasses such that quantum size effects are significant. Transparent and colorless gels were prepared through the hydrolysis of a complex solution of Si(OC2H5)4, (CH3)2SO, Zn(CH3COO)2 · 2H2O and Cd(CH3COO)2 · 2H2O. These gels were heated at 350, 500 and 750°C. The thermal treatments of samples were established by TDA/TGA analysis. By means of shift in optical absorption spectra, quantum size effects could be inferred in glasses containing these calcogenide microcrystals.