The new PEI(poly(epoxy-imide))-nano Silica film has been synthesized via in situ CS sol process, and the chemical bonding and microstructure of nano silica dispersed in resin were examined by FT-IR, TAG and SEM. The dielectric properties of these hybrid films over a given temperature and frequency ranges have been studied in a point of view of stable chemical bonding of nano Silica filler. The results from IR spectra and SEM photograph indicated that PEI-Silica hybrid film prepared with nano CS sol process has been synthesized in uniform and chemical bonding. The decrease property of dielectric constant with CS content, tangent loss consistent of given frequency and temperature has been explained in terms of the chain movement of polymer through chemical bonging and size effect of nano silica. The new PEI-CS sol hybrid film with such stable chemical and dielectric properties was expected to be used as a high functional coating application in ET, IT and electric power products.