The sol-gel fabrication of new well-dispersed polyimide (PI)/TiO2 nanohybrid films is reported. The PI matrixes are synthesized via the polycondensation of pyromellitic dianhydride and a diamine monomer containing several constructive functional groups which introduced some interesting features to the final nanocomposite (NC) materials. The TiO2-heteroatom interactions associated with the flexible characteristic of polymer backbone (which facilitates the stated interactions) have been led to the fabrication of well-dispersed nanoparticles with less than 100 nm in sizes, as confirmed by means of transmission electron microscopy. Thermal analysis techniques (TGA and DSC) have shown the superior thermal stability of fabricated NCs. The UV-Vis spectroscopy has illustrated a growing trend in the absorption efficiency along with the increase in TiO2 contents. The created TiO2 nanoparticles showed amorphous structures according to the X-ray diffraction patterns.