The hollow nanofibers of Ce-0.8 Gd-0.2 O2-delta (GDC20) were electrospun from the PVP and nitrate precursors. The evolution of hollow channel was investigated by TG-DTA and ex situ TEM for the fibers heated at 250-300 degrees C for 1-5 h. The hollow cores were revealed during the crystallization of nano-GDC20 and the PVP decomposition stage. The structural and morphological properties of GDC20 fibers before and after being calcined at 500-900 degrees C for 8 h were investigated by FTIR, FE-SEM, TEM, EDS, XRD, and Raman spectroscopy. The results from XRD and Raman scattering verify the successful doping of Gd3+ ions into the CeO2 host lattice. The conductivity of the cold-pressed GDC 20 pellet sintered at 1400 degrees C is more than 0.01 S/cm at and above 600 degrees C.