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 situreduction 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.