Heterostructured SrTiO3/TiO2 nanofibers were fabricated by in situ hydrothermal Method using TiO2 nanofibers as both template and reactant. The as-fabricated heterostructures composite included SrTiO3 nanocubes or nano particles assembled uniformly on the surface of TiO2 nanofibers. Compared with the pure TiO2 nanofibers, SrTiO3/TiO2 nanofibers exhibited enhanced photocatalytic activity in the decomposition of Rhodamine B (RB) under ultraviolet light. The enhanced photocatalytic activity of SrTiO3/TiO2 nanofibers could be attributed to the improvement of charge separation derived from the coupling effect of TiO2 and SrTiO3 nanocomposite.