This study is reporting the role of embedded ferroelectric ceramics Bi4Ti3O12 (BTO = 1–5 wt%) into the polyvinylidene fluoride (PVDF) composites on its structural, bonding, surface morphology, and dielectric response. Especially lead free flexible composite electrodes have lot of attention due to its high dielectric permittivity and energy storage density. X‐ray diffraction spectra confirms monophasic orthorhombic structure of composites, while Fourier transform infrared (FTIR) spectra confirms the bonding behavior. Scanning electron microscopy (SEM) images surface morphology of homogeneously distributed ceramic particles with interconnected network. Dielectric constant has been found to be improved from 9.56 to 13.73 for BTO5%PVDF95% composites at frequency of 1 kHz attributes promoted interfacial polarization of PVDF and effectively limited the charge leakage in the composites, implying promising applications in flexible electronic devices.