Self-polarized Gd5Si4-polyvinylidene fluoride (PVDF) nanocomposite films have been synthesized via a facile phase-inversion technique. For the 5 wt% Gd5Si4-PVDF films, the enhancement of the piezoelectric β-phase and crystallinity are confirmed using Fourier transform infrared (FTIR) spectroscopy (phase fraction, Fβ, of 81% as compared to 49% for pristine PVDF) and differential scanning calorimetry (crystallinity, ΔXc, of 58% as compared to 46% for pristine PVDF), respectively. The Gd5Si4 magnetic nanoparticles, prepared using high-energy ball milling were characterized using Dynamic Light Scattering and Vibrating Sample Magnetometry (VSM) to reveal a particle size of ∼470 nm with a high magnetization of 11 emu/g. The VSM analysis of free-standing Gd5Si4-PVDF films revealed that while the pristine PVDF membrane shows weak diamagnetic behavior, the Gd5Si4-PVDF films loaded at 2.5 wt% and 5 wt% Gd5Si4 show enhanced ferromagnetic behavior with paramagnetic contribution from Gd5Si3 phase. The interfacial interactions between Gd5Si4 and PVDF results in the preferential crystallization of the β-phase as confirmed via the shift in the CH2 asymmetric and symmetric stretching vibrations in the FTIR. These results confirm the magnetic Gd5Si4 nanoparticles embedded in the PVDF membrane lead to an increased β-phase fraction, which paves the way for future efficient energy harvesting applications using a combination of magnetic and piezoelectric effects.