Currently, piezoelectric ceramics are being applied in various fields, such as ultrasonic sensors, vibration devices, sound filters, and various energy conversion devices. Flexible piezoelectric ceramics are widely studied in an effort to mitigate the disadvantages of their brittle and inductile properties. Structural damage to piezoelectric fibers is much less than that to thin films when piezoelectric fibers are twisted or bent. Therefore, stretchable devices can be fabricated if piezoelectric fibers are obtained using an elongated substrate. In this study, sintering processes of PZT ($Pb(Zr_{0.53}Ti_{0.47})O_3$) fibers prepared by electrospinning were optimized through the TGA and XRD analyses. The crystal structure and microstructure of the piezoelectric fibers were investigated by XRD, FE-SEM and TEM.