With the contemplations of ecological and environmental issues related to energy harvesting, piezoelectric nanogenerators (PNGs) may be an accessible, sustainable, and abundant elective wellspring of energy in the future. The PNGs' power output, however, is dependent on the mechanical energy input, which will be intermittent if the mechanical energy is not continuous. This is a fatal flaw for electronics that need continuous power. Here, a self-charging flexible supercapacitor (PSCFS) is successfully realized that can harvest sporadic mechanical energy, convert it to electrical energy, and simultaneously store power. Initially, chemically processed multimetallic oxide, namely, copper cobalt nickel oxide (CuCoNiO4) is amalgamated within the poly(vinylidene fluoride) (PVDF) framework in different wt % to realize high-performance PNGs. The combination of CuCoNiO4 as filler creates a notable electroactive phase inside the PVDF matrix, and the composite realized by combining 1 wt % CuCoNiO4 with PVDF, coined as PNCU 1, exhibits the highest electroactive phase (>86%). Under periodic hammering (∼100 kPa), PNGs fabricated with this optimized composite film deliver an instantaneous voltage of ∼67.9 V and a current of ∼4.15 μA. Furthermore, PNG 1 is ingeniously integrated into a supercapacitor to construct PSCFS, using PNCU 1 as a separator and CuCoNiO4 nanowires on carbon cloth (CC) as the positive and negative electrodes. The self-charging behavior of the rectifier-free storage device was established under bending deformation. The PSCFS device exhibits ∼845 mV from its initial open-circuit potential ∼35 mV in ∼220 s under periodic bending of 180° at a frequency of 1 Hz. The PSCFS can power up various portable electronic appliances such as calculators, watches, and LEDs. This work offers a high-performance, self-powered device that can be used to replace bulky batteries in everyday electronic devices by harnessing mechanical energy, converting mechanical energy from its environment into electrical energy.