Ultrafine one-dimensional LaFeO3 nanofibers were synthesized by electrospinning utilizing sol-gel precursors. The surface morphology, microstructure and crystal structure were investigated by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The nanofibers with smaller diameter were continuous and uniformly distributed. Typical fiber diameter was between 180 nm and 220 nm and the average diameter was 200 nm. The fibers consisted of many single-crystal LaFeO3 grains and the grain size was about 20-50 nm. The relationship between the diameter of as-synthesized fibers and the PVP concentration of the precursor was investigated. The experimental results indicated that the PVP concentration had a great impact on the fiber size and 5.89 wt.% PVP concentration in sol-gel precursors was advantageous to the formation of more uniform electrospun composite fibers with smaller diameter. (C) 2010 Elsevier B.V. All rights reserved.