Abstract: With tetraethoxysilane (TEOS) as precursor, SiO₂/collagen hydrolysate-poly(vinyl alcohol) hybrid composite films (SiO₂/CH-PVA hybrid films) were in-situ prepared using a sol-gel technique. The influences of SiO₂ on properties of hybrid films were investigated by means of swelling, thermogravimetry, FTIR spectroscopy, SEM diagram and tensile tests. The results show that the addition of SiO₂ decreases the swelling ratio at equilibrium of hybrid films, slows down the swelling process, and effectively restricts the solubility of collagen hydrolysate in aqueous solution. Both adsorption peaks of Si—O—Si and Si—C in FTIR graphs indicate the formation of organic polymer/inorganic hybrid system, and SiO₂ significantly improves thermal properties and mechanical properties of the hybrid films, with the increase of the SiO₂ mass fractions from 0% to 20%, tensile strength of the hybrid film increases from 18 MPa to 25 MPa, and the elongation at break increases from 510% to 780%.