ZnO/carbon-TiO2 core-sheath nanofibrous film was fabricated by a combination of electrospinning, tetrabutyl titanate (TBT) treatment and heated treatment. The results of field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction revealed that the wurtzite ZnO nanoparticles were successfully incorporated in carbon nanofibers (NFs) matrix without aggregation. And a uniform TiO2 layer consisting of anatase and rutile covered on the surface of the ZnO/C NFs. The ZnO/C-TiO2 core-sheath NFs film was used to photodegrade rhodamine B and exhibited the photocatalytic efficiency of 98.8%, which was much higher than that of ZnO NFs and ZnO/C NFs. This might be attributed to the ZnO/C-TiO2 core-sheath structure with high separation efficiency of photo-generated electrons and holes. Moreover, ZnO/C-TiO2 core-sheath NFs could be easily recycled without decrease of photocatalytic activity.