Pb(Zr 0.5 Ti 0.5 )O 3 (PZT) piezoelectric ceramic fibers were prepared by using electrospun PZT/poly(vinyl acetate) (PVAc) composite fibers by calcination for 1 h at the temperature range of 500 °C–700 °C in air. The morphology and crystal structure of calcined PZT nanofibers were characterized as a function of calcination temperature with an aid of XRD, FT-IR, SEM, and TEM. XRD and FT-IR results revealed that pyrochlore phase began to appear after calcination at 500 °C. For the fibers calcined at 550–600 °C, the dominant phase of tetragonal perovskite PZT with a weak pyrochlore phase was detected. The pyrochlore and tetragonal perovskite phases coexisted for the fibers calcined at 650–700 °C. The morphology of the fibers has changed from a smooth and uniform fiber to a porous fiber with increasing the temperature. The optimized fibers with a diameter of 334 nm were obtained when the fibers were calcined at 550 °C.