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.