Size-controlled single-crystal-like lead zirconate titanate (PbZr0.52Ti0.48O3, PZT) ceramic fibers have been successfully prepared by sol-gel based electrospinning and subsequent calcination process, and their morphology, crystal structure have been characterized at nanoscale. The fiber diameter can be precisely controlled from similar to 50 to 540 nm by varying the PVP concentration and electrospinning process parameters. The crystal structure of the nanofibers pyrolyzed at 400 degrees C for 0.5 h and calcined at 650 degrees C for 2 h is proved to be single-crystal-like tetragonal perovskite phase. A formation mechanism is also discussed based on the thermal decomposition process, effect of the calcination and pyrolysis procedure, using the thermogravimetry/differential scanning caborimetry (TG/DSC), X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is found that the pyrolysis procedure is a critical factor for the fabrication of single-crystal-like structure PZT nanofibers using electrospinning. (C) 2013 Elsevier B.V. All rights reserved.