Flexible piezoelectric materials have promising prospects in the field of piezoelectric nanogenerators and self-powered devices. However, the poor piezoelectricity is the major obstacle hindering their practical application. Here, we prepared organic-inorganic hybrid perovskite (OIHP) ferroelectric nanorods as reinforcement to enhance the piezoelectricity of poly(vinylidene fluoride) (PVDF) nanofibers. The OIHP possess strong piezoelectricity and can facilitate the nanofibers to obtain outstanding electromechanical response. With the addition of OIHP, the PENG device fabricated by electrospinning nanofibers can achieve a significant output. The output voltage and short-circuit current of the nanogenerator are up to 40.3 V and 0.89 μA, respectively, which are almost 3-fold enhancement compared with pure PVDF. This work provides a feasible approach to prepare composite nanofibers with great piezoelectricity.