We report a flexible, ultrathin, and compact poly­(vinylidene fluoride)-based self-polarized piezoelectric nanogenerator via an expeditious quenching approach of the active layer. The appearance of the β phase of PVDF after quenching resulted in its applicability in energy harvesting. The employed organic solvents during the fabrication process contributed to the observance of the β phase, which is confirmed by X-ray diffraction and Fourier transform infrared spectroscopy. A two-step approach fabrication of the PVDF device showed exceptional performance, resulting in an open-circuit peak-to-peak voltage of 19.2 V upon human hand pressing and short-circuit current >0.7 μA. Also, the average d 33 value for the quenched PVDF film is observed to be −15.16 ± 5.81 pm/V. Further, charging of a capacitor and powering the liquid crystal displays (LCDs) are realized through the nanogenerator, thus validating mechanical energy conversion, storage, and powering applications.