Parallel arrays of ZnO/polyvinylidene fluoride (PVDF) microfibers were successfully prepared by low-voltage near-field electrospinning. The ZnO/PVDF microfiber arrays were characterized by optical microscope, scanning electron microscope(SEM) and energy dispersive X-ray spectroscopy(EDS). The average diameter of the composite fibers was about 40 mu m. The EDS analysis demonstrated that ZnO nanoparticles have been doped into the parallel microfibers. Some related piezoelectric properties and electrical properties are presented in this paper. The piezoelectric properties of the ZnO/PVDF microfiber arrays are enhanced, and the mechanism is discussed briefly. These results indicate that the low-voltage near-field electrospun ZnO/PVDF composite microfibers have potential application in piezoelectric pressure sensors and nanogenerators.