Recently, many researchers focus on the nanoscale fillers to enhance electrical properties of composite due to the uniqueness of material. In this study, polyimide/barium titanate (BaTiO3) nanofibers films were prepared by incorporating electrospun BaTiO3 nanofibers with polyimide derived from 2,2-Bis [4-(4-aminophenoxy)phenyl]propane (BAPP) and 3,3',4,4'-Biphenyl tetracarboxylic dianhydride (BPDA). The obtained nanofibers were modified with (3-Glycidyloxypropyl)trimethoxysilane as coupling agent before integrating into the polyimide matrix. Microstructure and dielectric properties of BaTiO3 nanocomposites were investigated. The results showed BaTiO3 nanofibers were successfully produced at nanoscale regime and well dispersed in the hybrid film after modification and ultrasonication method. Dielectric constant of the nanofibers films were improved and increased with increasing of BaTiO3 nanofibers concentration while dielectric loss remains relative low.