Electrospinning technique was used to fabricate PVP/Ce(NO 3) 3 composite microfibers. 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 °C and 600 nm at 800 °C) were smaller than those of PVP/Ce(NO 3) 3 composite fibers (1–2 μm). CeO 2 hollow nanofibers were obtained at 600 °C and CeO 2 hollow and porous nanofibers formed by nanoparticles were obtained at 800 °C. The length of the CeO 2 hollow nanofibers was greater than 50 μm. 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 M3m when calcination temperatures were 600–800 °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.