Piezoelectric nanogenerators(PENGs)that can harvest mechanical energy from ambient environment have broad prospects for multi-functional applications.Here,multi-layered piezoelectric composites with a porous structure based on highly oriented Pb(Zr0.52Ti0.48)O3/PVDF(PZT/PVDF)electrospinning fibers are prepared via a laminating method to construct high-performance PENGs.PZT particles as piezoelectric reinforcing phases are embedded in PVDF fibers and facilitate the formation of polar β phase in PVDF.The multi-layered,porous structure effectively promotes the overall polarization and surface bound charge density,resulting in a highly efficient electromechanical conversion.The PENG based on 10 wt％PZT/PVDF composite fibers with a 220 μm film thickness outputs an optimal voltage of 62.0 V and a power of 136.9 μW,which are 3.4 and 6.5 times those of 10 wt％PZT/PVDF casting film-based PENG,respectively.Importantly,the PENG shows a high sensitivity of 12.4 V·N-1,presenting a significant advantage in comparison to PENGs with other porous structures.In addition,the composites show excellent flexibility with a Young\'s modulus of 227.2 Mpa and an elongation of 262.3％.This study shows a great potential application of piezoelectric fiber composites in flexible energy harvesting devices.