Electrospinning was employed to produce homogeneous inorganic-organic composite fibers from alcohol solutions containing polyvinyl butyral (PVB) and precursor of yttrium and cerium ions. Upon heat treatment, ceria and yttria-doped ceria fibers were obtained. The fibers retained the original morphology observed in the as-spun composition. X-ray diffraction was used to identify the crystalline phases of the final products. Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and BET analysis were employed to study the ceramic-phase formation and the morphological evolution of the fibers. Thus, uniform ceria and yttria-doped ceria fibers several micrometers long of high-phase purity were produced. The CeO2 and the CeO2 with Y2O3 fibers presented average diameters that ranged from 0.8 to 1.7m, and the distribution of specific surface ranged from 24 to 127m2/g after heat treatment at 1000C.