Studies of composite films incorporating inorganic materials are of immense importance for current technological applications. Polyimide (PI) composite thin films incorporating indium tin oxide (ITO) at various weight ratios were processed using an in situ generation approach. The resultant product was imidized up to 350 • C to test the ability of the material to endure high temperatures without affecting the host matrix. The morphological behaviour of the PI/ITO composite films was investigated using Fourier transform infrared, scanning electron microscopy and atomic force microscopy characterization techniques. The degrees of crystallinity and ITO particle size within the PI matrix were studied using X-ray diffraction. The thermal, structural and electrical properties were analysed using thermogravimetric analysis, differential scanning calorimetry, UV-visible spectroscopy and the four-probe technique. The micromechanical properties of the composites were evaluated in terms of tensile strength, tensile modulus and elongation. 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 and PI, where ITO becomes dispersed and interacts within the PI matrix. This leads to a decrease in available free-space volume and increases the surface enrichment providing reinforcement to the matrix.