Ultra-fine Pb(Zr-0.3, Ti-0.7)O-3 (PZT) fibers with diameters down to similar to 100 nm have been synthesized by combing the sol-gel method and elecrospinning technique. The as-spun nanoscopic PZT/PVP composite fibers were annealed for 30 min at different temperatures, respectively. The morphology and crystalline structure of the sintered Pb(Zr0.3Ti0.7)O-3 (PZT) nanofibers were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), micro-Raman spectroscopy. The ferroelectronic and piezoelectric properties of single PZT nanofiber are investigated by using piezoresponse force microscopy (PFM). The results showed that the well crystallized PZT fibers with diameter of similar to 100 nm can achieve a d(33) of similar to 83.4 pm/V, which is much larger than that of the reported PZT thin film, and the domain can be successfully switched, with the switch domain polarity of about 180 degrees. All these show promise for new nanoscale ferroelectronic devices. (C) 2012 Elsevier B.V. All rights reserved.