A simple electrospinning method was used to fabricate polymer/inorganic composite fibers from solutions containing polyacrylonitrile (PAN) and BiCl3, and PAN and Bi(NO3)(3), respectively. By performing a calcining process for the composite fibers at 500 degrees C for 10 h, BiOCl and Bi2O3 nanofibers were successfully prepared. The as-prepared BiOCl and Bi2O3 nanofibers exhibit tetragonal and P phase, respectively. The photocatalytic test shows that BiOCl and Bi2O3 nanofibers possess photocatalytic properties with regard to decomposing rhodamine B under ultraviolet light. (c) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.