In this study, we report the synergistic role of (3-aminopropyl)triethoxysilane (APTES) functionalization of zinc oxide (ZnO) nanoparticles and low-temperature phase-inversion for boosting the polar β-phase of the poly(vinylidene fluoride) (PVDF) nanocomposite. The electroactive crystal phase was investigated with Fourier transform infrared, wide-angle X-ray diffraction, differential scanning calorimetry, dielectric spectroscopy, and dynamic contact mode electrostatic force microscopy. Our results confirm an enhanced polar β-phase and crystallinity, which inherently boosted the overall dielectric, ferroelectric, and piezoelectric properties of the PVDF/ZnO-APTES nanocomposite. The energy-harvesting potential of the nanocomposite was investigated by fabricating a piezoelectric device. The fabricated device with a high electroactive phase (PDVF/ZnO-APTES) exhibited a voltage of 125 V and an instantaneous output power density of ∼83 mW/cm 3 . The fabricated device can glow 8 lightemitting diodes (LEDs), blink 50 LEDs and could be a potential candidate for energy-scavenging applications.