Piezoelectric materials have attracted much attention due to their broad application areas and excellent electromechanical properties. PVDF-TrFE has good tensile properties, flexibility and biocompatibility, and is currently a popular piezoelectric polymer material in the field of flexible wearable electronics. Numerous studies have shown that the β-phase content in electrostatically spun PVDF-TrFE nanofibers is higher than that in cast films, so the use of electrostatic spinning to improve the piezoelectric properties of PVDF-TrFE is particularly effective. In this paper, high-performance PVDF-TrFE/ZnO nanofibers were prepared by electrostatic spinning. The stretching effect of electric field force and the growth of ZnO nanorods during the preparation process promoted the formation of piezoelectric β-phase of PVDF-TrFE, while the PVDF-TrFE fibers were compounded with ZnO nanorods, which also have piezoelectricity, to further enhance the piezoelectric properties of the material. The morphological characteristics of the prepared composite nanofiber films were analyzed by field emission scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and contact angle measurement. The electrical properties of the prepared composite nanofibers were measured by charge amplifier and oscilloscope, and the signal characteristics of the devices were collected under different action conditions. The results show that the composite materials have significantly higher electrical signal output, excellent sensitivity, and stable output in practical applications. the PVDF-TrFE composite fiber membranes also have the characteristics of softness and flexibility, light weight, and simple and controllable preparation, which can be applied to flexible devices and wearable devices, etc.