We use an ab-initio approach to analyze the structural, electronic band structure, and thermoelectric properties of titanium dioxide (TiO2 in rutile phase), and we then use rutile-TiO2 nanoparticles to determine its effects on sol-gel-produced polyvinyl alcohol/silicon dioxide (PVA/SiO2) hybrid films. The synthesis of hybrid films involved the incorporation of 1 % rutile-TiO2 nanoparticles in the PVA/SiO2 matrix. The thermoelectric properties of the resulting hybrid films were characterized by Seebeck coefficient measurements, as well as electrical and thermal conductivities. The synthesis of PVA/SiO2/Nano-TiO2 films was accomplished with success. The chemical bonds have amply demonstrated that the PVA backbone is connected to the (SiO2-TiO2) network. TGA testing indicates that hybrid films are more resistant to higher temperatures than pure PVA films. SiO2 nanoparticles reveal more effective loading to improve dielectric characteristics compared to TiO2. The best results are obtained in cases of mechanical, thermal and electrical insulation when both nanofillers are integrated into the polymer matrix. The findings show that the thermoelectric performance of PVA/SiO2 hybrid films is improved by the addition of (1 %) rutile-TiO2 nanoparticles in the rutile phase. This study provides insights into the potential applications of rutile-TiO2 nanoparticles in enhancing the thermoelectric properties of hybrid materials and opens up avenues for further research in this area, and contributes to the growing body of knowledge on enhancing the thermoelectric properties of materials by incorporating rutile-TiO2 nanoparticles into hybrid films synthesized by the sol-gel method.