Polyacrylonitrile(PAN)/manganese acetate(Mn(CH3COO)(2)) composite nanofibers have been fabricated by electrospinning, a simple and effective technology. The obtained composite nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). The composite nanofibers are amorphous in structure, continuous, even and smooth. At the same time, the reduction performance of Cr(VI) by oxalic acid in the presence of the composite nanofibers is also investigated. The results indicate that the composite nanofibers have exhibited excellent catalysis performance for Cr(VI) reduction from a Cr2O72--containing solution by oxalic acid. And the critical parameters, such as the catalyst dosage, oxalic acid content, chromium concentration, the pH value of the reaction solution and light have important impact on the reduction process. Under the simulated solar light irradiation, after only 60min, 1.2 mM initial Cr(VI) solution was reduced absolutely in the presence of PAN/Mn(CH3COO)(2) composite nanofibers containing 17.5 wt.% Mn(CH3COO)(2) by 0.3 mL 0.5 M oxalic acid. In light, the reduction of Cr(VI) by oxalic acid is markedly accelerated. (c) 2012 Elsevier B.V. All rights reserved.