This work is focused on the preparation and characterization of poly (vinyl alcohol)/silica gel/Nano-TiO2, and the study of titanium dioxide (TiO2) nanoparticles (from 1 to 5%) on the properties of poly (vinyl alcohol) (PVA)/silica films. This new material was prepared by the sol-gel method using poly (vinyl alcohol) powder with Tetraethyl Orthosilicate (TEOS) as a precursor source of silica. TEOS was hydrolyzed and condensed in water and ethanol in the presence of hydrochloric acid (HCl) used as a catalyst. Fourier transform infrared (FT-IR), water absorption, water contact angle, ultraviolet-visible spectrometry (UV-VIS), and thermogravimetric analysis (TGA) were used to characterize the hybrid films obtained. The PVA/SiO2/Nano-TiO2 films were successfully synthesized. Owing to the FT-IR Analysis, the chemical bonds have clearly shown that the PVA backbone is linked to the (SiO2-TiO2) network. UV-VIS tests indicated that the hybrid films' UV shielding properties were drastically enhanced as a result of the addition of TiO2. According to the TGA tests, the hybrid films are more heat tolerant than neat PVA films. The water contact angle results revealed that TiO2 nanoparticles used as a doping compound possess an important influence on the hydrophilicity of PVA/SiO2 as thin films. The film's water resistance has also been enhanced.