Combining the versatility of the electrospinning technique and hydrothermal growth of nanostructures enabled the fabrication of hierarchical SnO2/TiO2 Composite nanostructures. The results revealed that not only were secondary SnO2 nanostructures successfully grown on primary TiO2 nanofiber substrates but also the SnO2 nanostructures were uniformly distributed without aggregation on TiO2 nanofibers. By adjusting fabrication parameters, the morphology as well as coverage density of secondary SnO2 nanostructures could be further controlled, and then SnO2/TiO2 heterostructures with SnO2 nanoparticles or nanorods were facilely fabricated. The photocatalytic studies suggested that the SnO2/TiO2 heterostructures showed enhanced photocatalytic efficiency of photodegradation of Rhodamine B (RB) compared with the bare TiO2 nanofibers under UV light irradiation.