One-dimensional ZnO/CeO2 nanomaterial with high porosity was fabricated by calcination of the coaxial electrospun polyvinylpyrrolidone nanofibers containing zinc acetate and cerium nitrate precursors. The morphologies and microstructures of ZnO/CeO2 fibers were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Results reveal that the phase structures of ZnO/CeO2 fibers are composited by hexagonal (wurtzite) phase of ZnO and cubic (fluorite) phase of CeO2 with the particle size of about 10-15 nm. The experiments of photocatalytic activity indicate the ZnO/CeO2 porous nanofibers exhibit excellent photocatalytic performance in the degradation of rhodamine B. Ninety percent of rhodamine B molecules are decomposed by ZnO/CeO2 porous nanofibers in 90 min, which is much faster than by nanofibers of ZnO/CeO2 or single component of ZnO and CeO2. The high performance in photocatalytic catalysis for the ZnO/CeO2 nanofibers can be attributed to the improvement of separation of photogenerated electron-hole pairs, large surface area and the enhancement of adsorption ability of surfaces and interfaces in nanograined ZnO/CeO2 composites. (C) 2012 Elsevier B.V. All rights reserved.