In this study, lead zirconate titanate (PZT) nanofibers were synthesized by electrospinning method using polyvinylpyrrolidone (PVP) as a viscosity controller and were characterized the crystallinity and the chemical composition of PZT nanofibers obtained by different postannealing methods. From the X-ray photoelectron spectroscopy results, the formation of PZT nanofibers was confirmed. The diameter of PZT nanofibers was a few hundreds of nanometers. And the diameter of PZT-D (directly annealed to the target temperature) nanofibers decreased as the annealing temperature increased while the diameter of PZT-S (stepwisely annealed to the target temperature) nanofibers increased which were confirmed by SEM. According to the results of X-ray diffraction, as the annealing temperature increased, the crystallinity of PZT nanofibers changed from pyrochlore to perovskite structure and the perovskite phase of PZT was observed from the PZT nanofibers annealed at 823K.