In this work, a novel photocatalyst, polypyrrole (PPy)-decorated Ag-TiO2 nanofibers (PPy-Ag-TiO2) with core-shell structure, was successfully synthesized using an electrospinning technique, followed by a surfactant-directed in situ chemical polymerization method. The results show that a PPy layer was formed on the surface of Ag-TiO2 nanofiber, which is beneficial for protecting Ag nanoparticles from being oxidized. Meanwhile, the PPy-Ag-TiO2 system exhibits remarkable light absorption in the visible region and high photocurrent. Among them, the 1%-PPy-Ag-TiO2 sample shows the highest photoactivity, which is far exceeds that of the single- and two-component systems. This result may be due to the synergistic effect of Ag, PPy, and TiO2 nanostructures in the ternary system.