Herein, Ag/TiO2/Fe2TiO5 nanofiber composites with different contents of Ag were prepared using electrospinning with a calcining process. The structure and morphology of Ag/TiO2/Fe2TiO5 were characterized by TG-DTA, FT-IR, XRD, and SEM. The results shown that the organic template was completely decomposed at about 670 degrees C. It can also find the rutile and anatase TiO2 coexisted in TiO2 nanofibers, but the peaks of anatase TiO2 disappeared in Fe2TiO5/TiO2. In addition, when Ag added in the Fe2TiO5/TiO2, the peaks of Fe2TiO5 and TiO2 have been strengthened greatly. It can conclude that the Fe3+ and Ag+ have an opposite effect on the crystal growing of the sample. In addition, the Ag nanoparticles (AgNPs) were well distributed in the surface of TiO2/Fe2TiO5. The UV-Vis DRS and electrochemical tests indicated that the light absorption and carries separation of Ag/TiO2/Fe2TiO5 were enhanced obviously. Since the surface plasmon resonance effect of AgNPs and synergistic effect, the as-prepared composite (the content of Ag was 3% mol) show a higher photocatalytic performance in degradation of Rhodamine B (RhB 99.6%) than that of pure-TiO2 and TiO2/Fe2TiO5.