A series of organic/inorganic hybrid (OIH) films were prepared using cellulose acetate (CA) as the organic component and tetraethyl orthosilicate (TEOS) as the inorganic component. The chemical, morphological, and mechanical properties of these films were evaluated with a variety of analytical techniques. The results of these evaluations showed that crosslinked CA OIH films were formed during the sol-gel reactions. The structure of OIH films was very sensitive to the CA/TEOS ratio and film formation conditions. All of the films with added TEOS were two phase on a molecular level i.e., inorganic TEOS domains surrounded by a CA matrix. Under some film formation conditions the presence of TEOS, a nonsolvent for CA, led to solvent/nonsolvent phase separation on the micron scale.