Composite-based piezoelectric devices are extensively studied to develop sustainable power supply and selfpowered devices owing to their excellent mechanical durability and output performance. In this study, we design a leadfree piezoelectric nanocomposite utilizing (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 (BCTZ) nanomaterials for realizing highly flexible energy harvesters. To improve the output performance of the devices, we incorporate porous BCTZ nanowires (NWs) into the nanoparticle (NP)-based piezoelectric nanocomposite. BCTZ NPs and NWs are synthesized through the solidstate reaction and sol-gel-based electrospinning, respectively; subsequently, they are dispersed inside a polyimide matrix. The output performance of the energy harvesters is measured using an optimized measurement system during repetitive mechanical deformation by varying the composition of the NPs and NWs. A nanocomposite-based energy harvester with 4:1 weight ratio generates the maximum open-circuit voltage and short-circuit current of 0.83 V and 0.28 A, respectively. In this study, self-powered devices are constructed with enhanced output performance by using piezoelectric energy harvesting for application in flexible and wearable devices.