Eco-friendly, nontoxic and high-energy storage materials are very important for flexible electrode materials. Bi4Ti3O12 lead-free, perovskite phase may prove suitable as filler in composites for electrode materials because of its large spontaneous polarization. We have synthesized Bi4Ti3O12/polystyrene (BTO/PS) composites and carried out their structural, morphological and bonding studies with the help of X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), in that order. Dielectric measurements in the broad frequency range of synthesized composites determined by Impedance analyzer. We observed that the dielectric constant of composites increased with filler concentration and decreased with applied field frequency. Bi4Ti3O12/PS composites can be good electrode materials.