Photocatalysis of TiO2 has recently drawn considerable attention, while the photoefficiency of TiO2 is limited by its large band-gap energy and usually fast electron-hole recombination. Here, we present an unconventional heterostructure of Ag nanoparticles modified TiO2 nanofibers synthesized by one-step electrospinning process, to improve the photoefficiency of TiO2 host. The efficient promotion of the visible light photocatalysis of Ag/TiO2 nanofiber heterostructures can be ascribed to the electronic excitation of Ag nanoparticles under visible light and the transfer of the electrons to TiO2 conduction band, which deeply depends on the number of Ag/TiO2 junctions and the height of Schottky barrier. The Ag/Ti molar ratio can be easily controlled by the electrospinning process and the Ag/TiO2 nanofibers with Ag/Ti molar ratio of 0.05 exhibit the highest photocatalytic activity. Simultaneously, the Ag/TiO2 nanofiber heterostructures show excellent photocatalytic stability. (C) 2013 AIP Publishing LLC.