Inorganic nano-composite polyimide (PI) films were prepared with the method of sol-gel. The interfacial situation and the fractal characteristics of PI films were investigated by small angle X-ray scattering (SAXS) using synchrotron radiation as X-ray source. SAXS results indicated that the scattering curves in the high-angle region have a negative slope, i.e., a negative deviation from Porod's law, which suggests that there are obvious interface layers between the organic phase and the inorganic phase in the PI films. The thicknesses of interface layers are 0.54—1.48 nm. The interaction of the organic phase and inorganic phase becomes stronger and the thickness of interfacial layer increases with the increase of inorganic nano-components. Nano-particles have mass fractal, simultaneously have surface fractal structure, and their distribution and assemblage are nonlinear dynamic processes. With the inorganic nano-components increasing, the surface fractal dimension increases and mass fractal dimension decreases, which shows that the nano-particles structure becomes looser and mass distribution becomes more uneven. The anchoring action of polymer chains is enhanced and the number of anchored point increased respectively, the surface of the hybrid PI films becomes rougher. Finally, according to the interface characteristics of hybrid PI films, the relationship of the breakdown field strength with component is analyzed by percolation theory and polarization theory.