Polyimide/layered silicate films can be used to protect semiconductor chips against gas and moisture permeation to prevent corrosion followed by failure of the electronic chip. The layered silicates in these films are used as barrier pigment to extend the diffusion pathway and to improve the barrier properties. However, the exfoliation of the silicates has an essential impact on the quality of the barrier. Films prepared from polyimide matrix with layered silicates were investigated as well as the distribution and orientation of silicate particles in the UV-cured film and the correlative mechanisms while hardening. The films were characterized by a variety of methods including SEM, FTIR, TGA, water vapor diffusion (WVD) and oxygen permeation measurement. The prepared films using polyimide / layered silicates nanocomposites showed a reduction of WVD and oxygen permeation of 30% and 80%, respectively. Results demonstrated that polyimide/layered silicate nanocomposite could be used as barrier coating to reduce the permeation of moisture and gases.