Core/shell nanofibers of TiO2@carbon embedded by Ag nanoparticles (TiO2@C/Ag NFs) were fabricated by combining the electrospinning technique, the hydrothermal method and an in situ reduction approach. The results showed that a uniform graphite carbon layer of approximately 8 nm in thickness was formed around the electrospun TiO2 nanofiber and small Ag nanoparticles (Ag NPs) were dispersed well inside the carbon layer. And, the TiO2@C/Ag NFs had remarkable light absorption in the visible region. The photocatalytic studies revealed that the TiO2@C/Ag NFs exhibited enhanced photocatalytic efficiency of photodegradation of Rhodamine B (RB) and Methyl Orange (MO) compared with the pure TiO2 nanofibers, TiO2@carbon core/shell nanofibers and TiO2/Ag nanofibers under visible light irradiation, which might be attributed to the good light absorption capability and high separation efficiency of photogenerated electron-hole pairs based on the photosynergistic effect among the three components of TiO2, carbon and Ag. And, the TiO2@C/Ag NFs could be easily recycled due to their one-dimensional nanostructural property.