Poly(vinylidene fluoride) (PVDF) is processed at high temperature to generate energy from waste mechanical energy. The piezoelectric β-phase has been induced through uniaxial elongation of polymer films at high temperature. The extent of β-phase has been confirmed from a deconvoluted XRD pattern, found to be ∼75% of the electroactive phase, and able to demonstrate high piezoelectric effect as evident from the measured piezoelectric coefficient of −30 pC/N after a suitably processed and poled specimen. Bulk morphology and spectroscopic studies support the structural alteration. Following the direct piezoelectric effect, energy harvesting devices have been fabricated which show very high power output of 55.2 μW/cm² using the processed and poled specimen. Thus, robust and easily processable polymeric material having very high energy conversion efficiency is demonstrated which is sufficient to power miniaturized devices.