Self-assembled hybrid organo-silica sol-gel materials are rapidly expanding for new and novel applications. The microporous solid silica matrix was used as a carrier for the controlled release of ascorbic acid (AA), selected as cargo molecule. One-step synthesis procedure was optimized for the preparation of silica–molecule composites by using tetraethoxysilane and methyltrimethoxysilane as precursors. The hydrophobic silica xerogel matrices were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. Specific surface area and porosity parameters were determined by Brunauer-Emmett-Teller (BET) technique and the matrix surface morphology by scanning electron microscopy (SEM). The observed release pattern could be interesting for the development of AA-fortified food and for use in food packaging.