Bi2O3 nanofibers with diameter of 70-200 nm were successfully prepared by electrospinning a precursor mixture of polyacrylonitrile (PAN)/bismuth nitrate, followed by calcination treatment of the electrospun polymer/inorganic composite fibers. The resulting Bi2O3 nanofibers were characterized with X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, FT-IR spectra and UV-vis diffuse reflectance spectroscopy. The Bi2O3 nanofibers calcined at 500 degrees C exhibited beta phase, and whereas the nanofibers calcined at 550 and 600 degrees C both exhibited dominant 6 phase together with a trace amount of alpha phase. Photocatalytic experiments indicated that the obtained Bi2O3 nanofibers calcined at 500 degrees C were highly active for photodegradation of organic pollutants Rhodamine B (RB). Furthermore, the Bi2O3 nanofibers could be easily recycled without decrease of the photocatalytic activity. (c) 2009 Elsevier Inc. All rights reserved.