Excellent dielectric property and amazing X-ray Diffraction spectra were found for the novel polyimide films by composing SiO2 hollow spheres with different wt%. The dielectric constants of that from different dianhydrides were ranged of 1.9-3.1 at 1MHz. It was sure that the dielectric constants of the films could be tunable in wider range with different wt% SiO2 hollow sphere as well as different dianhydrides. And in the X-ray Diffraction spectra, some films not only presented wide diffractive peaks of amorphous structures, but also showed sharp crystal peaks at 58.7o and 28.4o. And the Intensity of the sharp crystal peak was dramatically related with the value of dielectric constants. It might be caused by the ordered structure in part of polymer chain. And the structures and properties of the composite thin films were also measured with scanning electron microscope and dynamic themomechanical analysis et al.