Studies of polymeric ternary composite thin films incorporating inorganic materials are of immense importance for current technological applications. Polyimide (PI) composite thin films incorporating indium tin oxide (ITO) and poly (vinlylidene fluoride) (PVDF) at various weight ratios were processed using an in situ generation approach with the spin coating unit. The resultant product was imidized up to 350º C to test the ability of the material to endure high temperatures without affecting the host matrix. The structural and morphological behavior of the PVDF/ ITO/ PI composite films was investigated using Fourier Transform Infrared, Scanning Electron Microscopy and Atomic Force Microscopy characterization techniques. The degrees of crystallinity and PVDF/ ITO particle size within the PI matrix were studied using X-ray diffraction. The electrical properties were analyzed using Differential Scanning Calorimetry, UV-visible spectroscopy and the four-probe technique. An overall improvement in the properties of the composite films was observed in comparison to those of pure PI. The synergistic improvement in the composite films is associated with the interaction mechanism between ITO/ PVDF with PI, where ITO becomes dispersed and interacts within the PI and PVDF compound matrix. This leads to a decrease in available free-space volume and increases the surface enrichment providing reinforcement to the matrix.