The V2O5/TiO2 nanoheterostructures with high photocatalytic activity in visible light region are synthesized via electrospinning directly. Photodecomposition rate of RhB by V2O5/TiO2 nanoheterostructures is much faster than that using of pure TiO2 nanofibers. Furthermore, the influence of V/Ti molar rate on visible light photocatalysis is studied. Experimental results indicate that optimum V/Ti molar rate of V2O5/TiO2 nanoheterostructures is found to be about 1:1. It can be attributed to the fewer efficient V2O5/TiO2 heterostructures formed in the V2O5/TiO2 nanofibers when the V/Ti molar rates deviate from 1:1. In addition, the V2O5/TiO2 nanoheterostructures show excellent photocatalytic stability after 10 cycles under visible light irradiation. (C) 2012 Elsevier B.V. All rights reserved.