Piezoelectric energy harvesting technologies, which can be used to convert the electricity from the mechanical energy, have been developed in order to assist or power the wearable electronics. To realize non-toxic and biocompatible electronics, the lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 (BCTZ) nanoparticles (NPs) are being studied with a great attention as flexible energy harvesting device. Herein, piezoelectric hybrid nanocomposites were fabricated using BCTZ NPs-embedded poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] matrix to improve the performance of flexible energy harvester. Output performance of the fabricated energy device was investigated by the well-optimized measurement system during the periodically bending and releasing motions. The generated open-circuit voltage and the short-circuit current of the piezoelectric hybrid nanocomposite-based energy harvester reached up to ~15 V and ~1.1 μA, respectively; moreover, the instantaneous power of 3.5 μW is determined from load voltage and current at the external load of 20 MΩ. This research is expected to cultivate a new approach to high-performance wearable self-powering electronics.