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 nanowalls growing on the primary TiO2 nanofibers. Interestingly, not only were secondary CeO2 nanowalls successfully grown on TiO2 nanofibers substrates, but also the CeO2 nanowalls were uniformly distributed without aggregation on TiO2 nanofibers. The photocatalytic studies suggested that the CeO2/TiO2 heterostructures showed enhanced photocatalytic efficiency compared with bare TiO2 nanofibers under UV light irradiation.