Electroactive poly(vinylidene fluoride) (PVDF) thin films modified with Ce(NO₃)₃·6H₂O and Y(NO₃)₃·6H₂O (1–30 mass%) have been prepared via a simple solution casting method. The thermal stability and microstructures of the films were investigated using thermal gravimetric analysis techniques and field emission electron microscopy respectively. X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy and differential scanning calorimetry confirmed the nucleation of the electroactive β phase in the composite films. Strong interfacial interaction i.e. ion dipole interaction via formation of hydrogen bonds between the water molecules of the salts and the polar –CF₂ dipoles of the polymer chains resulted in improved electroactive β phase nucleation and a large dielectric constant in PVDF films.