One-dimensional BiFeO₃/TiO₂ heterostructure nanofibers with high visible-light photocatalytic activity have been successfully obtained via a facile hydrothermal process followed by an electrospinning technique. The results show that the BiFeO₃/TiO₂ nanofibers are as long as dozens of micrometers with the diameters of about 100–300 nm, where BiFeO₃ nanoparticles are surrounded by anatase-type TiO₂ nanocrystals. Compared with the corresponding pure BiFeO₃ nanoparticles, and TiO₂ nanofibers, the as-prepared BiFeO₃/TiO₂ nanofibers exhibit a markedly enhanced photocatalytic activity in the degradation of methyl blue under visible light irradiation. The enhanced photocatalytic activity is attributed to the formed p–n heterojunction between BiFeO₃ and TiO₂, which results in synergistic enhancement. Notably, the BiFeO₃/TiO₂ nanofibers could be easily recycled without the decrease in the photocatalytic activity because of their one-dimensional nanostructural property. With their high degradation efficiency and fine recyclability, the BiFeO₃/TiO₂ heterostructure nanofibers will have wide application in photodegradation of various organic pollutants.