Titanium dioxide/polyvinylidene fluoride (TiO2/PVDF) composite was prepared by electrospinning process to enhance the dielectric properties for application as a gate insulator in organic thin-film transistors (OTFTs). Scanning electron microscopy, thermogravimetric analysis, and X-ray diffraction were employed to characterize the as-prepared samples, and then their dielectric constants were investigated by impedance analysis. The impedance results show that the dielectric constant of the electrospun TiO2/PVDF nanofibers is higher than those of other samples, demonstrating that electrospun TiO2/PVDF composite can be a proper candidate for gate insulators in OTFTs.