Heterostructured semiconductor nanostructures have provoked great interest in the areas of energy, environment and catalysis. Herein, we report a novel hierarchical Ag3PO4/TiO2 heterostructure consisting of nearly spherical Ag3PO4 particles firmly coupled on the surface of TiO2 nanofibers (NFs). The construction of Ag3PO4/TiO2 heterostructure with tailored morphologies, compositions and optical properties was simply achieved via a facile and green synthetic strategy involving the electrospinning and solution-based processes. Owing to the synergetic effects of the components, the resulting hybrid heterostructures exhibited much improved visible light photocatalytic performance, which could degrade the RhB dye completely in 7.5 min. In addition, the coupling of Ag3PO4 particles with UV-light-sensitive TiO2 NFs enabled full utilization of solar energy and less consumption of noble metals, significantly appealing for their practical use in new energy sources and environmental issues. The developed synthetic strategy was considered to be applicable for the rational design and construction of other heterostructured catalysts. (C) 2015 Elsevier B.V. All rights reserved.