Polyimide (PI)/silica (SiO2) nanohybrid composite waveguide films prepared from Pyromellitic dianhydride (PMDA), 2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FHP), nonlinear optical (NLO) molecule, coupling agent APTES and hydrolysate of TEOS via sol-gel process and thermal imidization. The silicacontent in the hybrid waveguide films varied from 0 to 22.5/wt%. The PI hybrids prepared were characterized by IR, thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), etc. They exhibit fair good optical transparency. The SiO2 phase is well dispersed in the polymer matrix. DSC and TGA results show that these hybrid waveguide materials have excellent thermal stability.