We demonstrated a generic strategy for the synthesis of Ag/TiO2 nanofibers by combining electrospinning technology and solvothermal route. Products were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectra, X-ray diffraction. The formation mechanism of Ag/TiO2 nanofibers was presented and the possible mechanism relating to photocatalytic performance was discussed in detail. The investigation of photocatalytic ability showed that Ag/TiO2 nanofibers possess an excellent photocatalytic activity superior to pure TiO2 nanofibers for the degradation of Rhodamine B. Additionally, the recycling experiment of Ag/TiO2 nanofibers had been done, demonstrating that Ag/TiO2 nanofibers have high efficiency and stability.