Electrospinning technique was used to fabricate PVP/Ce(NO(3))(3) composite nucrofibers. Different morphological CeO(2) nanofibers were obtained by calcination of the PVP/Ce(NO(3))(3) composite microfibers and were characterized by scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), thermal gravimetric and differential thermal analysis (TG-DTA), and (FTIR). SEM micrographs indicated that the surface of the composite fibers was smooth and became coarse with the increase of calcination temperatures. The diameters of CeO(2) hollow nanofibers (300 nm at 600 degrees C and 600 nm at 800 degrees C) were smaller than those of PVP/Ce(NO(3))(3) composite fibers (1-2 mu m). CeO(2) hollow nanofibers were obtained at 600 degrees C and CeO(2) hollow and porous nanofibers formed by nanoparticles were obtained at 800 degrees C. The length of the CeO(2) hollow nanofibers was greater than 50 mu m. XRD analysis revealed that the composite microfibers were amorphous in structure and CeO(2) nanofibers were cubic in structure with space group O(H)(5) - F(M 3 m) when calcination temperatures were 600-800 degrees C. TG-DTA and FTIR revealed that the formation of CeO(2) nanofibers was largely influenced by the calcination temperatures. Possible formation mechanism of CeO(2) hollow nanofibers was proposed.