Polyimide (PI)/mica hybrid films were successfully prepared by in situ condensation polymerization method, in which the mica particles were modified by coupling agent γ-aminopropyltriethoxy silane (APTS) to strengthen the interaction between the mica particles and PI matrix. The morphology, structure, thermal and mechanical properties as well as dielectric properties of PI films were systematically studied via Scanning electron microscope (SEM), Fourier transform infrared spectrometer (FT-IR spectrometer), Thermal gravimetric analysis (TGA), tensile experiments, Thermal mechanical analyzer (TMA), impedance analyzer, etc. The results indicated that the mica particles were dispersed homogeneously in PI matrix, leading to an improvement of the mechanical property, thermal stability and hydrophobicity. It was novel to notice that hybrid films exhibited low coefficient of thermal expansion (CTE) and low dielectric constant simultaneously. The CTE and dielectric constant of hybrid film dropped to 25.36 ppm/k and 2.42 respectively, in the presence of 10 wt% mica into polyimide matrix.