One-dimensional TiO₂ nanofibers were synthesized using an electrospinning method. Subsequently, Ag₃PO₄/TiO₂ heterostructures were successfully fabricated through a simple deposition–precipitation reaction. The Ag₃PO₄/TiO₂ heterostructures exhibited enhanced photocatalytic performance under visible light. The improved photocatalytic activities are attributed to the visible light absorption enhanced by Ag₃PO₄ and the formation of a heterojunction between TiO₂ and Ag₃PO₄, which can effectively accelerate the charge separation and transfer. The heterostructures can be reclaimed easily by sedimentation without a decrease in the photocatalytic activity due to the large length to diameter ratio of the nanofiber framework.