Combining the versatility of electrospinning technique and hydrothermal growth of nanostructures enabled the fabrication of hierarchical CeO2/TiO2 nanofibrous mat. The as-prepared hierarchical heterostructure consisted of CeO2 nanostructures growing on the primary TiO2 nanofibers. Interestingly, not only were secondary CeO2 nanostructures successfully grown on TiO2 nanofibers substrates, but also the CeO2 nanostructures were uniformly distributed without aggregation on TiO2 nanofibers. By selecting different alkaline source. CeO2/TiO2 heterostructures with CeO2 nanowalls or nanoparticles were facilely fabricated. The photocatalytic studies suggested that the CeO2/TiO2 heterostructures showed enhanced photocatalytic efficiency of photodegradation of dye pollutants compared with bare TiO2 nanofibers under UV light irradiation. (C) 2010 Elsevier Ltd. All rights reserved.