PVDF and PVDF/BaTiO₃ nanocomposite films are studied in the present work. BaTiO₃ (BTO) nanoparticles have been synthesized using a cost-effective sol–gel method, while free-standing PVDF/BaTiO₃ nanocomposite films with varying BaTiO₃ content have been prepared using the solvent casting technique. Phase identification has been carried out using the X-ray diffraction technique. The direct bandgap of all films was calculated using the Kubelka–Munk (KM) function. Two distinct peaks were observed in KM function vs. energy plots for PVDF/BTO nanocomposite films corresponding to PVDF and BaTiO₃. An increase in the magnitude of the dielectric constant is observed in PVDF/BaTiO₃ nanocomposite films compared to pure PVDF. Room temperature ferroelectric response is studied at two different frequencies of 10 and 400 Hz. Non-saturated ferroelectric loops are observed in PVDF and PVDF/BTO films, indicating the lossy capacitor behaviour. An increase in maximum polarization is observed with the addition of BTO nanoparticles, attributed to interfacial effects and interactions between nanoparticles.